EP3152253B1 - Diphenylguanidine-free rubber compositions comprising short-chained alkyl esters of glycerol - Google Patents

Diphenylguanidine-free rubber compositions comprising short-chained alkyl esters of glycerol Download PDF

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EP3152253B1
EP3152253B1 EP15724733.9A EP15724733A EP3152253B1 EP 3152253 B1 EP3152253 B1 EP 3152253B1 EP 15724733 A EP15724733 A EP 15724733A EP 3152253 B1 EP3152253 B1 EP 3152253B1
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phr
rubber
particularly preferably
rubber mixture
mixture according
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French (fr)
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EP3152253A1 (en
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Ulrich Feldhues
Heinz Unterberg
Hermann-Josef Weidenhaupt
Melanie WIEDEMEIER-JARAD
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/40—Thiurams, i.e. compounds containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to rubber mixtures containing a maximum of 1 phr diphenylguanidine and each containing at least one rubber, a silica-based filler and / or carbon black and short-chain alkyl esters of glycerol and 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ), their production and use, as well as the vulcanizates thereby obtainable by the vulcanization process, in particular in the form of tires, parts of tires or technical rubber articles.
  • the networking of rubbers with sulfur accelerator systems has the advantage that the processing and product properties can be varied over a wide range by using different accelerators and their combinations, such as setting the induction period (scorch time) and the Response speed.
  • So-called secondary accelerators can be added to the rubber mixtures to regulate the induction and vulcanization times.
  • the best-known second accelerators are the guanidine accelerators. They are slow-acting accelerators with which the on (scorch) and / or curing time can be adjusted. In rubber mixtures they are used, for example, with 2 phr based on the active ingredient.
  • the tension value characteristic of rubber mixtures with guanidines shows a slow increase and reaches the maximum relatively late.
  • these accelerators result in a relatively unfavorable flow time / heating time ratio and show a relatively strong reversion in the rubber compound, so that they are often in combinations with primary accelerators, such as sulfenamide-based accelerators.
  • slow-acting accelerators have an important function in the production of fuel-saving silica tires. They interact with the silanol groups and reduce the filler interactions and the viscosity. They also counteract the retarding effect of acidic fillers.
  • DPG diphenylguanidine
  • WO 2013/104492 describes a rubber mixture containing 0.65 phr DPG and 2 phr polyols such as TMP.
  • FR 2984898 describes mixtures containing less than 0.45 phr DPG and 0.4 phr aminoether alcohols (such as 2- (2-aminoethoxy) ethanol).
  • FR 2984897 describes mixtures containing less than 0.5 phr DPG and less than 0.45 phr ether amines such as 3- (2-ethylhexyloxy) propylamine.
  • FR 2984895 describes mixtures containing less than 0.5 phr DPG and about 3.0 phr alkali metal hydroxides and / or alkaline earth metal hydroxides.
  • FR 2984896 describes mixtures containing less than 0.5 phr DPG and less than 8 phr of a primary amine such as hexadecylamine.
  • solubility parameter (MPa) 1/2 EPDM (ethylene / propylene / diene / rubber) 16.1 NR (natural rubber) 16.5 BR (butadiene rubber) 17.1 SBR (styrene / butadiene rubber) 17.6 CR (chloroprene rubber) 19.0 NBR (acrylonitrile butadiene rubber) 19.0 Plasticizers Glycerol triacetate (triacetin) 22.0 * * By converting the value for triacetin of 10.77 cal / m3 according to EP 1813310 with the factor 1 cal / m3 2.0455 MPa.
  • the object of the present invention is to provide essentially rubber mixtures free of diphenylguanidine, which are understood to mean mixtures which have a maximum of 1 phr, preferably less than 0.7 phr, particularly preferably less than 0.4 phr, and very particularly preferably less than 0 , 1 phr of diphenylguanidine, the properties relevant to the application, in particular the scorch time (MS-t5), Mooney viscosity, elongation at break, tensile strength, hardness and abrasion, being not significantly worse than mixtures containing diphenylguanidine.
  • the rubber mixtures should particularly preferably comprise non-polar rubbers.
  • the unit phr stands for parts by weight based on the rubber content in the rubber mixture defined as 100 parts by weight.
  • the short-chain alkyl ester of glycerol of the formula (I) can be added alone or together with one or more further mixture components in any order, even at higher temperatures in the range from 80 ° C to 200 ° C, preferably at a temperature of about 150 ° C.
  • rubber mixtures are essentially free of diphenylguanidine if the content of diphenylguanidine is 1 1 phr, preferably ⁇ 0.7 phr, particularly preferably ⁇ 0.4 phr and very particularly preferably ⁇ 0.1 phr.
  • the total content of diphenylguanidine and other guanidine derivatives in the rubber mixtures or vulcanizates according to the invention is 1 1 phr, preferably ⁇ 0.7 phr, particularly preferably ⁇ 0.4 phr, most preferably ⁇ 0.1 phr.
  • the rubber mixture according to the invention contains neither diphenylguanidine nor other guanidine derivatives.
  • the content of cellulose and / or cellulose derivatives is typically, which includes, in particular, reaction products of cellulose with phenyl isocyanate, n-butyric anhydride, acetic anhydride, butyl isocyanate, stearyl chloride, stearyl isocyanate or butyric acid chloride, but preferably cellulose acetate, in the rubber mixtures or vulcanizates according to the invention. preferably ⁇ 0.5 phr, particularly preferably ⁇ 0.1 phr and most preferably 0 phr.
  • the rubber mixture according to the invention can advantageously be used both in zinc-free and in zinc-containing rubber vulcanizates.
  • Triacetin is preferably used as the compound of formula (I).
  • the rubber mixture according to the invention contains from 0.1 to 40 phr, preferably from 0.2 to 20 phr, particularly preferably from 0.5 to 15 phr, very particularly preferably 1 to 12 phr, further preferably 2 to 10 phr and most preferably 3 to 8 phr of compounds of formula (I).
  • Rubber mixtures according to the invention and rubber vulcanizates according to the invention can also contain further known rubber additives.
  • the rubber mixture according to the invention contains the anti-reversion agent 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ).
  • the rubber mixture contains 0.1 to 15 phr of the anti-reversion agent 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS number 151900-44-6 ), preferably 0.1-2 phr, particularly preferably 0.2-1.0 phr.
  • the additive of the formula (I) is preferably added in the first part of the mixing process at, for example, melt temperatures of 100-250 ° C., but it can also be used later at lower temperatures (40-100 ° C.), for example together with sulfur and / or accelerator.
  • the additive of the formula (I) and the addition of 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane CAS No .: 151900-44-6 ) preferably in the first part of the mixing process at, for example, melt temperatures of 100-250 ° C, but it can also be done later at lower temperatures (40-100 ° C), for example together with sulfur and / or accelerator.
  • the additive of the formula (I) and / or 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) independently of one another both in pure form and on an inert, organic or inorganic support, preferably a support selected from the group comprising natural or synthetic silicates, in particular neutral, acidic or basic silica, aluminum oxide, carbon black or zinc oxide and / or attached thereto adsorbed.
  • the additive of the formula (I) can also be admixed with 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) be added to the mixing process.
  • the rubber mixtures according to the invention are particularly suitable for the production of tire treads, subtreads, carcasses and apex mixtures.
  • Tires or tire parts also include, for example, treads from summer, winter and all-season tires, and treads from car and truck tires.
  • Another aspect of the present invention are vulcanizates obtainable by vulcanizing the rubber mixture according to the invention.
  • the rubber vulcanizates produced are suitable for the manufacture of various rubber products, for example for the manufacture of tire components, in particular for tire treads, subtreads, carcasses, sidewalls, reinforced sidewalls for run-flat tires, apex mixtures, etc., and for the manufacture of technical rubber articles such as damping elements, roller coverings, coverings for conveyor belts, belts , Spinning cops, seals, golf ball cores, shoe soles, etc.
  • the rubber products according to the invention can impart advantageous operating properties to motor vehicles equipped with them in particular. Such motor vehicles are therefore also the subject of the present invention.
  • the rubber mixture according to the invention contains at least one non-polar rubber selected from the group consisting of NR, SBR, BR, IR, SIBR, IIR, ENR and EPDM, preferably from the group consisting of NR, SBR, BR, IR, IIR, ENR and EPDM, further preferably from the group consisting of NR, SBR, BR, IIR and EPDM, particularly preferably from the group consisting of NR, BR and SBR, the total content of these nonpolar rubbers in the rubber mixture at least 50 phr, preferably at least 60 phr and particularly preferably is at least 70 phr. In a particularly preferred embodiment, the total content of these non-polar rubbers is at least 80 phr, preferably at least 90 phr, more preferably at least 95 phr and particularly preferably at least 99 phr.
  • the mixtures according to the invention can also contain polar rubbers, in particular rubbers with a solubility parameter of more than 17.6.
  • the content of polar rubbers in the form of NBR, HNBR, HXNBR and XNBR in the rubber mixture is typically less than 10 phr, preferably less than 1.0 phr, particularly preferably less than 0.1 phr and very particularly preferably less than 0.01 phr.
  • the silicas and silicates mentioned can also be present in silanated form, which are obtained by treatment with chlorosilanes such as monochlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane, organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyltrichlorosilanesilane (meth) trichlorosilanesilane (meth) trichlorosilane (meth) chlorosilane (meth) trichlorosilane (meth) chlorosilane (meth) trichlorosilane and methane chlorosilane or silanes containing alkoxy groups such as acryloxypropyltrimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-glycidoxypropyltrimeth
  • carbon blacks can be used, in particular carbon blacks which have a BET surface area of 20-200 m 2 / g, such as SAF-, ISAF, are suitable for this purpose, produced using the flame black, furnace or gas black process -, IISAF, HAF, FEF or GPF carbon blacks are used.
  • the total content of fillers in the rubber mixture according to the invention can in principle be varied within any limits. Usual amounts are 0.1 to 200 phr, preferably 30 to 150 phr. In a preferred embodiment, the content of soot-based fillers is lower than that of silica-based fillers.
  • rubber mixtures and rubber vulcanizates according to the invention can contain one or more sulfur-containing silanes and or one or more crosslinking agents.
  • Sulfur-based or peroxidic crosslinking agents are particularly suitable for this, with sulfur-based crosslinking agents being particularly preferred.
  • the rubber mixture according to the invention can be used in any amount of so-called reclaim rubber, as is used, for example, in CN101628994 is used.
  • Preferred sulfur-containing silanes for the rubber mixture and rubber vulcanizates according to the invention are bis (triethoxysilylpropyl) tetrasulfane and disulfane and 3- (triethoxysilyl) -1-propanethiol or silanes such as Si 363 from Evonik, Germany or Silan NXT or NXT Z from Momentive (formerly GE, USA), the alkoxy radical being methoxy or ethoxy, in amounts of 2 to 20 parts by weight, preferably 3-11 parts by weight, each calculated as a 100% active ingredient and based on 100 parts by weight. Parts of rubber, in question. Mixtures of these sulfur-containing silanes can also be used.
  • Liquid sulfur-containing silanes can be mounted on a carrier for better meterability and / or dispersibility (dry liquid).
  • the active substance content is preferably between 30 and 70 parts by weight, preferably 40 and 60 parts by weight per 100 parts by weight of dry liquid.
  • the present rubber mixtures contain 50 to 100 phr of silica-based filler and 0.2 to 12 phr of organic silanes, preferably sulfur-containing organic silanes, particularly preferably alkoxysilyl-containing and very particularly preferably trialkoxy-silyl group-containing sulfur-containing organic silanes.
  • additives include triallyl isocyanurate, triallyl cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate , Trimetylolpropane tri (meth) acrylate, zinc diacrylate, zinc dimethacrylate, 1,2-polybutadiene or N, N'-m-phenylene-dimaleinimide are suitable.
  • Sulfur can be used as a crosslinker in elemental soluble or insoluble form or in the form of sulfur donors.
  • sulfur donors are dimorpholyl disulfide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulfide, dipentamethylene thiuram tetrasulfide (DPTT), tetramethylthiuram disulfide (TMTD) and tetrabenzylthiuram disulfide (TBzTD).
  • the rubber mixture contains 0.1-15 phr TBzTD, preferably 0.1-2 phr, particularly preferably 0.1-0.5 phr.
  • the rubber mixture according to the invention can be crosslinked with sulfur or sulfur donors alone, or together with vulcanization accelerators, for which purpose e.g. Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthates, bi- or polycyclic amines, dithiophosphates, caprolactams and thiourea derivatives are suitable. Zinc-diamine diisocyanate, hexamethylenetetramine, 1,3-bis (citraconimidomethyl) benzene and cyclic disulfanes are also suitable.
  • the rubber mixtures according to the invention preferably contain sulfur-based crosslinking agents and vulcanization accelerators.
  • Sulfur, magnesium oxide and / or zinc oxide to which the known vulcanization accelerators such as mercaptobenzothiazoles, thiazole sulfenamides, thiurams, thiocarbamates, xanthates and thiophosphates are added, are particularly preferably used as crosslinking agents.
  • crosslinking agents and vulcanization accelerators are preferably used in amounts of 0.1 to 10 phr, particularly preferably 0.1 to 5 phr, in the rubber mixture according to the invention.
  • the rubber mixture according to the invention and the vulcanized rubber according to the invention can contain further rubber auxiliaries, such as, for example, adhesion systems, anti-aging agents, heat stabilizers, light stabilizers, antioxidants, in particular ozone protection agents, flame retardants, processing aids, impact strength improvers, Plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators, in particular triethanolamine, polyethylene glycol, hexanetriol and anti-reversion agents.
  • adhesion systems such as, for example, adhesion systems, anti-aging agents, heat stabilizers, light stabilizers, antioxidants, in particular ozone protection agents, flame retardants, processing aids, impact strength improvers, Plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators, in particular triethanolamine, polyethylene glycol, hexanet
  • rubber auxiliaries are used in conventional amounts, which u. a. according to the intended use of the vulcanizates. Usual amounts are 0.1 to 30 phr.
  • Preferred anti-aging agents are alkylated phenols, styrenated phenol, sterically hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert. -butyl-4-ethylphenol, sterically hindered phenols containing ester groups, thioether-containing sterically hindered phenols, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) (BPH) and sterically hindered thiobisphenols.
  • BHT 2,6-di-tert-butylphenol
  • BHT 2,6-di-tert-butyl-p-cresol
  • BPH 2,6-di-tert. -butyl-4-ethylphenol
  • sterically hindered phenols containing ester groups 2,2'-methylene-bis- (4-methyl
  • amine anti-aging agents e.g. Mixtures of diaryl-p-phenylenediamines (DTPD), octylated diphenylamine (ODPA), phenyl- ⁇ -naphthylamine (PAN), phenyl- ⁇ -naphthylamine (PBN), preferably those based on phenylenediamine, e.g. B.
  • DTPD diaryl-p-phenylenediamines
  • ODPA octylated diphenylamine
  • PAN phenyl- ⁇ -naphthylamine
  • PBN phenyl- ⁇ -naphthylamine
  • phosphites such as tris (nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), 2-mercaptobenzimidazole (MBI), methyl-2-mercaptobenzimidazole (MMBI), zinc methyl mercaptobenzimidazole (ZMMBI) , which are mostly used in combination with the above phenolic anti-aging agents.
  • TMQ, MBI and MMBI are mainly used for NBR rubbers, which are vulcanized peroxidically.
  • the ozone resistance can be improved by antioxidants such as N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine (7PPD), N, N '-Bis- (1,4-dimethylpentyl) -p-phenylenediamine (77PD), enol ethers or cyclic acetals can be improved.
  • antioxidants such as N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine (7PPD), N, N '-Bis- (1,4-dimethylpentyl) -p-phenylenediamine (77PD), enol ethers or cyclic acetals can be improved.
  • Processing aids should act between the rubber particles and counteract frictional forces during mixing, plasticizing and shaping.
  • the rubber mixtures according to the invention can contain all lubricants customary for the processing of plastics, such as, for example, hydrocarbons, such as oils, paraffins and PE waxes, fatty alcohols with 6 to 20 carbon atoms, Ketones, carboxylic acids such as fatty acids and montanic acids, oxidized PE wax, metal salts of carboxylic acids, carboxylic acid amides and carboxylic acid esters, for example with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as the acid component.
  • the rubber mixture composition according to the invention can also contain flame retardants.
  • Antimony trioxide, phosphoric acid esters, chlorinated paraffin, aluminum hydroxide, boron compounds, zinc compounds, molybdenum trioxide, ferrocene, calcium carbonate or magnesium carbonate are used for this purpose.
  • the rubber mixture according to the invention and the rubber vulcanizate according to the invention can also be admixed with further plastics which act, for example, as polymeric processing aids or impact modifiers.
  • plastics are preferably selected from the group consisting of the homopolymers and copolymers based on ethylene, propylene, butadiene, styrene, vinyl acetate, vinyl chloride, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched or unbranched C1 to C10 alcohols, where polyacrylates with the same or different alcohol residues from the group of the C4 to C8 alcohols, in particular butanol, hexanol, octanol and 2-ethylhexanol, polymethyl methacrylate, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copoly
  • RFS direct adhesive systems are based on resorcinol, formaldehyde and silica, the so-called RFS direct adhesive systems. These direct adhesion systems can be used in any amount of the rubber mixture according to the invention, at any time when it is mixed into the rubber mixture according to the invention.
  • methylolamine derivatives are also suitable as formaldehyde donors.
  • a possible improvement in adhesion is achieved by adding components capable of forming synthetic resins, such as phenol and / or amines and aldehydes or aldehydes or compounds which split off the known rubber mixtures.
  • Resorzine and hexamethylenetetramine (HEXA) are widely used as resin-forming components in rubber adhesive mixtures GB-PS 801 928 , FR-PS 1 021 959 ), optionally in combination with silica filler ( DE-AS 1 078 320 ).
  • the rubber vulcanizate according to the invention can be used, for example, for the production of foams.
  • chemical or physical blowing agents are added.
  • Suitable chemical blowing agents are all substances known for this purpose, such as, for example, azodicarbonamide, p-toluenesulfonylhydrazide, 4,4'-oxybis (benzenesulfohydrazide), p-toluenesulfonylsemicarbazide, 5-phenyltetrazole, N, N'-dinitrosopentamethylenetetramine, zinc carbonate or sodium hydrogen carbonate and mixtures containing these substances.
  • Carbon dioxide or halogenated hydrocarbons for example, are suitable as physically active blowing agents.
  • the rubber mixtures according to the invention are typically vulcanized at temperatures of 100-250 ° C., preferably 130-180 ° C., a pressure of 10-200 bar possibly prevailing.
  • the present invention furthermore relates to the use of compounds of the formula (I) for the preparation of the rubber mixtures, vulcanizates and / or rubber products according to the invention.
  • the rubber vulcanizates according to the invention can be produced, for example, in the following mixing stages:
  • This mixing process can take place at temperatures of 100 to 170 ° C, preferably in the range of 150 ° C.
  • the mixing piece After completion of the first mixing stage, the mixing piece is taken up by a downstream rolling mill and shaped into a plate, a strip or pellets and stored for 24 hours at room temperature.
  • Processing temperatures are below 60 ° C.
  • pinching is carried out at 140 to 170 ° C., preferably at 150 ° C., for example in a kneader / internal mixer.
  • additives such as vulcanization accelerators and / or sulfur crosslinkers, preferably on a roller at low temperatures ( ⁇ 80 ° C).
  • Suitable units for the production of mixtures are known per se and include, for example, rollers, internal mixers or also mixing extruders.
  • Vulcanizates were produced from the rubber formulations listed in Table 1 for Examples 1 and 2 and for the reference examples.
  • the respective constituents of Examples 1 and 2 and of the reference examples were mixed in a multi-stage mixing process, as described below, and the mixtures were then vulcanized at 170 ° C.
  • This mixing process was carried out at a temperature of 150 ° C.
  • the mixing piece was taken up by a downstream rolling mill and formed into a plate and stored for 24 hours at room temperature.
  • Processing temperatures are below 60 ° C.
  • a pinch was carried out at 150 ° C. in a kneader.
  • the viscosity can be determined directly from the force that rubbers (and rubber mixtures) oppose to their processing.
  • Mooney shear disk viscometer a corrugated disk is enclosed at the top and bottom with sample substance and moved in a heatable chamber at about two revolutions per minute. The force required for this is measured as torque and corresponds to the respective viscosity.
  • the sample is usually preheated to 100 ° C for one minute; the measurement takes another 4 minutes, keeping the temperature constant.
  • the viscosity is specified together with the respective test conditions, for example ML (1 + 4) 100 ° C (Mooney viscosity, large rotor, preheating time and test time in minutes, test temperature).
  • the scorch behavior of a mixture can be measured with the same test as described above.
  • the selected temperature was 130 ° C.
  • the rotor runs until the torque value has risen to 5 Mooney units relative to the minimum value after passing through a minimum (t5).
  • the course of vulcanization on the MDR (moving the rheometer) and its analytical data are measured on a Monsanto rheometer MDR 2000 in accordance with ASTM D5289-95.
  • the time at which 95% of the rubber is crosslinked is determined as the vulcanization time.
  • the selected temperature was 170 ° C.
  • Dynamic test methods are used to characterize the deformation behavior of elastomers under periodically changing loads. External tension changes the conformation of the polymer chain.
  • the rubber mixtures according to the invention showed no dispersion problems. Little or no aniline is released during processing.

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Description

Die Erfindung betrifft Kautschukmischungen enthaltend maximal 1 phr Diphenylguanidin und enthaltend mindestens je einen Kautschuk, einen Kieselsäure-basierenden Füllstoff und/oder Ruß und kurzkettige Alkylester des Glyzerins sowie 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)-hexan ( CAS-Nr.: 151900-44-6 ), deren Herstellung und Verwendung, sowie die dadurch erhältlichen Vulkanisate nach dem Vulkanisationsverfahren, insbesondere in der Form von Reifen, Teilen von Reifen oder technischen Gummiartikeln.The invention relates to rubber mixtures containing a maximum of 1 phr diphenylguanidine and each containing at least one rubber, a silica-based filler and / or carbon black and short-chain alkyl esters of glycerol and 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ), their production and use, as well as the vulcanizates thereby obtainable by the vulcanization process, in particular in the form of tires, parts of tires or technical rubber articles.

Mit der Erfindung der Vulkanisation von Naturkautschuk wurde ein neuer Werkstoff geschaffen, dessen einzigartige Eigenschaften wesentlich zur Entwicklung der modernen Technik beigetragen hat. Zu Beginn des 20. Jahrhunderts erkannte man die beschleunigende Wirkung basischer organischer Verbindungen.With the invention of vulcanization of natural rubber, a new material was created, the unique properties of which contributed significantly to the development of modern technology. At the beginning of the 20th century, the accelerating effect of basic organic compounds was recognized.

Aus der DRP 265221 ist bekannt, dass Piperidin zur Beschleunigung der Vulkanisation im Naturkautschuk sowie in synthetisch hergestellten Kautschuken verwendet wurde. Piperidin war giftig, sehr flüchtig und es roch unangenehm, so dass die Kautschukverarbeitende Industrie basische Alternativen zu Piperidin suchte und einsetzte.It is known from DRP 265221 that piperidine has been used to accelerate vulcanization in natural rubber and in synthetically produced rubbers. Piperidine was toxic, very volatile, and smelled unpleasant, so the rubber processing industry looked for and used basic alternatives to piperidine.

In weiteren Patentveröffentlichungen werden beispielsweise Anilin und andere stickstoffhaltige organische Verbindungen wie Hexamethylentetramin, Thiocarbanilid als Beschleuniger beschrieben.Further patent publications describe, for example, aniline and other nitrogen-containing organic compounds such as hexamethylenetetramine, thiocarbanilide as accelerators.

Generell bietet die Vernetzung von Kautschuken mit Schwefel-Beschleuniger-Systemen den Vorteil, dass durch die Verwendung unterschiedlicher Beschleuniger und deren Kombinationen die Verarbeitungs- und Produkteigenschaften über einen weiten Bereich variiert werden können, wie beispielsweise die Einstellung der Induktionsperiode (Scorch-Zeit) und der Reaktionsgeschwindigkeit. Zur Regulierung der Induktions- und Vulkanisationszeit, können den Kautschukmischungen sogenannte Zweitbeschleuniger zugesetzt werden. Zu den bekanntesten Zweitbeschleunigern zählen die Guanidin-Beschleuniger. Sie sind langsam wirkende Beschleuniger, mit denen die An (Scorch)- und/oder Ausvulkanisationszeit angepasst werden kann. In Kautschukmischungen werden sie beispielsweise mit 2 phr bezogen auf den Wirkstoff eingesetzt.In general, the networking of rubbers with sulfur accelerator systems has the advantage that the processing and product properties can be varied over a wide range by using different accelerators and their combinations, such as setting the induction period (scorch time) and the Response speed. So-called secondary accelerators can be added to the rubber mixtures to regulate the induction and vulcanization times. The best-known second accelerators are the guanidine accelerators. They are slow-acting accelerators with which the on (scorch) and / or curing time can be adjusted. In rubber mixtures they are used, for example, with 2 phr based on the active ingredient.

Die Spannungswertcharakteristik von Kautschukmischungen mit Guanidinen zeigt einen langsamen Anstieg und erreicht relativ spät das Maximum. Diese Beschleuniger ergeben, alleine eingesetzt, ein verhältnismäßig ungünstiges Fließzeit/Heizzeit-Verhältnis und zeigen eine relativ starke Reversion im Kautschukcompound, so dass sie häufig in Kombinationen mit Primär-Beschleunigern, wie beispielsweise Sulfenamid-basierenden Beschleunigern, eingesetzt werden.The tension value characteristic of rubber mixtures with guanidines shows a slow increase and reaches the maximum relatively late. When used alone, these accelerators result in a relatively unfavorable flow time / heating time ratio and show a relatively strong reversion in the rubber compound, so that they are often in combinations with primary accelerators, such as sulfenamide-based accelerators.

Eine wichtige Funktion haben diese langsam wirkenden Beschleuniger in der Herstellung Treibstoff-sparender Silica-Reifen. Sie wechselwirken mit den Silanol-Gruppen und bewirken eine Reduktion der Füllstoff-Wechselwirkungen und der Viskosität. Sie steuern auch der verzögernden Wirkung saurer Füllstoffe entgegen.These slow-acting accelerators have an important function in the production of fuel-saving silica tires. They interact with the silanol groups and reduce the filler interactions and the viscosity. They also counteract the retarding effect of acidic fillers.

Eine der in der Kautschukindustrie bedeutendsten Guanidin-Typen ist das Diphenylguanidin (DPG). DPG ist weit verbreitet. Es ist dem Fachmann bekannt, dass DPG unter Vulkanisationsbedingungen Anilin freisetzt. Vor diesem Hintergrund suchen Anwender, die durch die Anilin-Problematik sensibilisiert sind, nach einem neuen Zweitbeschleuniger.One of the most important guanidine types in the rubber industry is diphenylguanidine (DPG). DPG is widely used. It is known to the person skilled in the art that DPG releases aniline under vulcanization conditions. Against this background, users who are sensitive to the aniline problem are looking for a new second accelerator.

In Patentoffenlegungen sind verschiedene DPG-reduzierte Mischungen beschrieben:
So wird in US 2010/0048775 , US 7605201 , US 6753374 und US 7714050 vorgeschlagen, in Kieselsäure-basierten Kautschukmischungen ganz oder teilweise die DPG-Menge durch ein spezielles Amin oder ein Thiuramdisulfid zu ersetzen.Various DPG-reduced mixtures are described in patent disclosures:
So in US 2010/0048775 , US 7605201 , US 6753374 and US 7714050 proposed to replace all or part of the amount of DPG in silica-based rubber mixtures with a special amine or a thiuram disulfide.

In WO 2013/104492 wird eine Kautschukmischung beschrieben, die 0,65 phr DPG und 2 phr Polyole wie beispielsweise TMP beinhaltet.In WO 2013/104492 describes a rubber mixture containing 0.65 phr DPG and 2 phr polyols such as TMP.

FR 2984898 beschreibt Mischungen, enthaltend weniger als 0,45 phr DPG sowie 0,4 phr Aminoether-Alkohole (wie beispielsweise 2-(2-Aminoethoxy)ethanol). FR 2984898 describes mixtures containing less than 0.45 phr DPG and 0.4 phr aminoether alcohols (such as 2- (2-aminoethoxy) ethanol).

FR 2984897 beschreibt Mischungen, enthaltend weniger als 0,5 phr DPG und weniger als 0,45 phr Ether-amine wie beispielsweise 3-(2-Ethylhexyloxy)propylamine. FR 2984897 describes mixtures containing less than 0.5 phr DPG and less than 0.45 phr ether amines such as 3- (2-ethylhexyloxy) propylamine.

FR 2984895 beschreibt Mischungen, enthaltend weniger als 0,5 phr DPG und ca. 3,0 phr Alkalimetalhydroxyde und/oder Erdalkalihydroxyde. FR 2984895 describes mixtures containing less than 0.5 phr DPG and about 3.0 phr alkali metal hydroxides and / or alkaline earth metal hydroxides.

FR 2984896 beschreibt Mischungen, enthaltend weniger als 0,5 phr DPG und weniger als 8 phr eines primären Amines wie beispielsweise Hexadecylamin. FR 2984896 describes mixtures containing less than 0.5 phr DPG and less than 8 phr of a primary amine such as hexadecylamine.

In den Veröffentlichungen wie beispielsweise in der US 2010/0048775 , US 7605201 , US 6753374 , US 7714050 , WO 2013/104492 , FR 2984898 , FR 2984897 , FR 2984895 und FR 2984896 wird jedoch nur auf eine gleichbleibende, zum Teil auf eine längere Scorch-Zeit eingegangen.In publications such as the US 2010/0048775 , US 7605201 , US 6753374 , US 7714050 , WO 2013/104492 , FR 2984898 , FR 2984897 , FR 2984895 and FR 2984896 however, only a constant, sometimes a longer scorch time will be dealt with.

Die Verwendung von Triacetin in Kautschukmischungen als "Lösungsmittel" für Cellulosederivate ist in EP 2604651 beschrieben, wobei die Zugabe von Triacetin und Cellulosederivaten aber zu verschlechterten Eigenschaften des Vulkanisats insbesondere des Abriebs führt.The use of triacetin in rubber mixtures as a "solvent" for cellulose derivatives is in EP 2604651 described, but the addition of triacetin and cellulose derivatives leads to deteriorated properties of the vulcanizate, in particular the abrasion.

Zudem sind in DE102010005558 Ether-Thioether bzw. Ester-Thioether enthaltende Weichmacherzubereitungen enthaltend Triacetin beschrieben und diese enthaltende polare Kautschukmischungen auf Basis von (H)NBR, CR, etc. In den Beispielen zeigte sich bei Verwendung von Triacetin gegenüber dem Vergleichsbeispiel eine leichte Verbesserung der Verarbeitungseigenschaften der Kautschukmischung, die aber mit einer Verschlechterung der Stoffeigenschaften des Vulkanisats einherging.In addition, in DE102010005558 Plasticizer preparations containing ether thioether or ester thioether containing triacetin and polar rubber mixtures based on (H) NBR, CR, etc. are described in the examples. When using triacetin compared to the comparative example, the processing properties of the rubber mixture were slightly improved, which was accompanied by a deterioration in the properties of the vulcanizate.

Insbesondere die Verwendung von Triacetin als Additiv in unpolaren Kautschuk-Typen ist nicht beschrieben und aufgrund der unterschiedlichen Löslichkeitsparameter für den Fachmann auch nicht erfolgversprechend, da es bei der Herstellung einer Kautschukmischung mit guten Eigenschaften darauf ankommt, dass die Komponenten verträglich sind. Laut Röthemeyer und Sommer ( Kautschuktechnologie, Hanser Verlag München Wien, 2. Ausgabe, 2006, ISBN-13: 978-3-446-40480-9, Seite 331-333 ) lässt sich anhand des Löslichkeitsparameters von Kautschuk und Weichmachern die Verträglichkeit des Weichmachers im Kautschuk abschätzen. Hierbei sollte in erster Annäherung die Differenz der Löslichkeitsparameter innerhalb von ± 10% liegen. In dem genannten Werk sind folgende Löslichkeitsparameter für Kautschuke angegeben: Kautschuk Löslichkeitsparameter (MPa)1/2 EPDM (Ethylen/Propylen/Dien/-Kautschuk) 16,1 NR (Naturkautschuk) 16,5 BR (Butadien-Kautschuk) 17,1 SBR (Styrol/Butadien-Kautschuk) 17,6 CR (Chloropren-Kautschuk) 19,0 NBR (Acrylnitril-butadien-Kautschuk) 19,0 Weichmacher Glycerintriacetat (Triacetin) 22,0* * Durch Umrechnung des Wertes für Triacetin von 10,77 cal/m3 gemäß EP 1813310 mit dem Faktor 1 cal/m3 = 2,0455 MPa. In particular, the use of triacetin as an additive in non-polar rubber types has not been described and, because of the different solubility parameters, is not promising for the person skilled in the art, since it is important that the components are compatible when producing a rubber mixture with good properties. According to Röthemeyer and Sommer ( Rubber technology, Hanser Verlag Munich Vienna, 2nd edition, 2006, ISBN-13: 978-3-446-40480-9, page 331-333 ) the compatibility of the plasticizer in the rubber can be estimated on the basis of the solubility parameter of rubber and plasticizers. In a first approximation, the difference in solubility parameters should be within ± 10%. The following solubility parameters for rubbers are specified in the named plant: rubber Solubility parameter (MPa) 1/2 EPDM (ethylene / propylene / diene / rubber) 16.1 NR (natural rubber) 16.5 BR (butadiene rubber) 17.1 SBR (styrene / butadiene rubber) 17.6 CR (chloroprene rubber) 19.0 NBR (acrylonitrile butadiene rubber) 19.0 Plasticizers Glycerol triacetate (triacetin) 22.0 * * By converting the value for triacetin of 10.77 cal / m3 according to EP 1813310 with the factor 1 cal / m3 = 2.0455 MPa.

Anhand der Lehre von Röthemeyer und Sommer erwartet der Fachmann, dass Triacetin generell in unpolaren Kautschuken, d.h. z.B. in Kautschuken mit einem Löslichkeitsprodukt von nicht mehr als 17,6 nicht gut löslich sein sollte, da die Differenz der Löslichkeitsprodukte bereits 20% beträgt.Based on the teaching of Röthemeyer and Sommer, the expert expects that triacetin generally in non-polar rubbers, i.e. e.g. should not be readily soluble in rubbers with a solubility product of no more than 17.6, since the difference between the solubility products is already 20%.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, im Wesentlichen Diphenylguanidin-freie Kautschukmischungen bereitzustellen, worunter Mischungen verstanden werden, welche maximal 1 phr, vorzugsweise weniger als 0,7 phr, besonders bevorzugt weniger als 0,4 phr, und ganz besonders bevorzugt weniger als 0,1 phr Diphenylguanidin aufweisen wobei die anwendungsrelevanten Eigenschaften, insbesondere die Scorchzeit (MS-t5), Mooney Viskosität, Bruchdehnung, Zugfestigkeit, Härte und Abrieb gegenüber Diphenylguanidin-haltigen Mischungen nicht wesentlich schlechter sind. Besonders bevorzugt sollten die Kautschukmischungen unpolare Kautschuke beinhalten. Die Einheit phr steht für Gewichtsteile bezogen auf den als 100 Gewichtsteile definierten Gehalt an Kautschuk in der Kautschukmischung.The object of the present invention is to provide essentially rubber mixtures free of diphenylguanidine, which are understood to mean mixtures which have a maximum of 1 phr, preferably less than 0.7 phr, particularly preferably less than 0.4 phr, and very particularly preferably less than 0 , 1 phr of diphenylguanidine, the properties relevant to the application, in particular the scorch time (MS-t5), Mooney viscosity, elongation at break, tensile strength, hardness and abrasion, being not significantly worse than mixtures containing diphenylguanidine. The rubber mixtures should particularly preferably comprise non-polar rubbers. The unit phr stands for parts by weight based on the rubber content in the rubber mixture defined as 100 parts by weight.

Durch Ersatz des Diphenylguanidins sollten Kautschukmischungen erhalten werden, welche toxikologisch weniger bedenklich sind und das Problem der Anilin-Emission reduzieren bzw. gar nicht erst entstehen lassen.By replacing the diphenylguanidine, rubber mixtures should be obtained which are less toxicologically harmful and reduce the problem of aniline emissions or prevent them from occurring in the first place.

Überraschend wurde nun gefunden, dass unter Verwendung kurzkettiger Alkylester des Glyzerins, mindestens je eines Kautschuks, eines Kieselsäure-basierenden Füllstoffs und/oder Ruß sowie 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)-hexan ( CAS-Nr.: 151900-44-6 ) Kautschukmischungen enthaltend maximal 1 phr Diphenylguanidin erhältlich sind, welche hervorragende Scorchzeiten (MS-t5) und verbesserte Abriebwerte bei guter Mooney Viskosität, Shore A Härte, Zugfestigkeit und Bruchdehnung aufweisen.Surprisingly, it has now been found that using short-chain alkyl esters of glycerol, at least one rubber each, a silica-based filler and / or carbon black and 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) Rubber mixtures containing a maximum of 1 phr diphenylguanidine are available, which have excellent scorch times (MS-t5) and improved abrasion values with good Mooney viscosity, Shore A hardness, tensile strength and elongation at break.

Besonders überraschend wurde gefunden, dass bei gemeinsamer Verwendung kurzkettiger Alkylester des Glyzerins zusammen mit dem Reversionsschutzmittel 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)hexan ( CAS-Nr. 151900-44-6 ) besonders niedrige Verlustfaktoren (tan delta 60°C) erhalten werden. Der Verlustfaktor (tan delta 60°C) ist ein Indikationswert für den Rollwiderstand. Je niedriger dieser Wert ist, desto niedriger ist der Rollwiderstand und damit übertragen auf den Autoreifen bzw. PKW, der Spritverbrauch.Particularly surprisingly, it was found that when short-chain alkyl esters of glycerol are used together with the anti-reversion agent 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS number 151900-44-6 ) particularly low loss factors (tan delta 60 ° C) can be obtained. The loss factor (tan delta 60 ° C) is an indication of the rolling resistance. The lower this value is, the lower the rolling resistance and thus the fuel consumption transferred to the car tire or car.

Die vorliegende Erfindung betrifft daher Kautschukmischungen enthaltend maximal 1 phr Diphenylguanidin und zumindest

  • einen unpolaren Kautschuk ausgewählt aus der Gruppe bestehend aus NR, SBR, BR, IR, SIBR, IIR, ENR und EPDM, bevorzugt NR, SBR, BR, IIR und EPDM, besonders bevorzugt NR, BR und SBR,
  • einen Kieselsäure-basierenden Füllstoff und/oder Ruß,
  • einen kurzkettigen Alkylester des Glycerins gemäß Formel (I)
Figure imgb0001
 worin
  • R1, R2, R3 unabhängig voneinander für Wasserstoff oder einen geradkettigen oder verzweigten C1-C4 -Alkylrest, vorzugsweise für einen Methylrest stehen und
  • - 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)-hexan ( CAS-Nr.: 151900-44-6 ),
    wobei der der Gesamtgehalt an unpolaren Kautschuken mindestens 50 phr und der Gehalt an Verbindungen der Formel (I) von 0,1 bis 40 phr beträgt.
The present invention therefore relates to rubber mixtures containing a maximum of 1 phr diphenylguanidine and at least
  • a non-polar rubber selected from the group consisting of NR, SBR, BR, IR, SIBR, IIR, ENR and EPDM, preferably NR, SBR, BR, IIR and EPDM, particularly preferably NR, BR and SBR,
  • a silica-based filler and / or carbon black,
  • a short-chain alkyl ester of glycerol according to formula (I)
Figure imgb0001
 wherein
  • R 1 , R 2 , R 3 independently of one another represent hydrogen or a straight-chain or branched C 1 -C 4 -alkyl radical, preferably a methyl radical, and
  • - 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ),
    wherein the total content of non-polar rubbers is at least 50 phr and the content of compounds of the formula (I) is from 0.1 to 40 phr.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von im Wesentlichen Diphenylguanidin-freien gefüllten Kautschukmischungen, bei welchem man jeweils mindestens

  • einen unpolaren Kautschuk ausgewählt aus der Gruppe bestehend aus NR, SBR, BR, IR, IIR, ENR und EPDM, bevorzugt NR, SBR, BR, IIR und EPDM, besonders bevorzugt NR, BR und SBR,
  • einen Kieselsäure-basierenden Füllstoff und/oder Ruß,
  • einen kurzkettigen Alkylester des Glycerins gemäß Formel (I)
Figure imgb0002
 worin
R1, R2, R3 unabhängig voneinander für Wasserstoff oder einen geradkettigen oder verzweigten C1-C4 -Alkylrest, vorzugsweise für einen Methylrest stehen, bei Massetemperaturen von 40 bis 200°C bevorzugt im Bereich von 80 bis 150°C mischt und anschließend nach Zugabe weiterer Vulkanisationschemikalien in üblicher Weise vulkanisiert. Typischerweise liegen die Scherraten bei der Mischung im Bereich von 1 - 1000 sec-1, bevorzugt 1 - 100 sec-1,Another object of the present invention is a process for the production of essentially diphenylguanidine-free filled rubber mixtures, in which at least one
  • a non-polar rubber selected from the group consisting of NR, SBR, BR, IR, IIR, ENR and EPDM, preferably NR, SBR, BR, IIR and EPDM, particularly preferably NR, BR and SBR,
  • a silica-based filler and / or carbon black,
  • a short-chain alkyl ester of glycerol according to formula (I)
Figure imgb0002
 wherein
R 1 , R 2 , R 3 independently of one another represent hydrogen or a straight-chain or branched C 1 -C 4 -alkyl radical, preferably a methyl radical, mixes at melt temperatures of 40 to 200 ° C, preferably in the range of 80 to 150 ° C, and then vulcanized in the usual manner after the addition of further vulcanization chemicals. The shear rates for the mixture are typically in the range from 1 to 1000 sec -1 , preferably 1 to 100 sec -1 ,

Die Zugabe des kurzkettigen Alkylesters des Glycerins der Formel (I) kann allein oder zusammen mit einem oder mehreren weiteren Mischungsbestandteilen in beliebiger Reihenfolge erfolgen, auch bei höheren Temperaturen im Bereich von 80°C bis 200 °C, bevorzugt bei einer Temperatur von ca. 150°C.The short-chain alkyl ester of glycerol of the formula (I) can be added alone or together with one or more further mixture components in any order, even at higher temperatures in the range from 80 ° C to 200 ° C, preferably at a temperature of about 150 ° C.

Im Sinne der Erfindung sind Kautschukmischungen im Wesentlichen Diphenylguanidinfrei sofern der Gehalt an Diphenylguanidin ≤ 1phr, vorzugsweise < 0,7 phr, besonders bevorzugt < 0,4 phr und ganz besonders bevorzugt < 0,1 phr beträgt.For the purposes of the invention, rubber mixtures are essentially free of diphenylguanidine if the content of diphenylguanidine is 1 1 phr, preferably <0.7 phr, particularly preferably <0.4 phr and very particularly preferably <0.1 phr.

In einer bevorzugten Ausführungsform beträgt der aufsummierte Gehalt an Diphenylguanidin und anderen Guanidin-Derivaten in den erfindungsgemäßen Kautschukmischungen bzw. Vulkanisaten ≤ 1phr, vorzugsweise < 0,7 phr, besonders bevorzugt < 0,4 phr, meist bevorzugt < 0,1 phr.In a preferred embodiment, the total content of diphenylguanidine and other guanidine derivatives in the rubber mixtures or vulcanizates according to the invention is 1 1 phr, preferably <0.7 phr, particularly preferably <0.4 phr, most preferably <0.1 phr.

In einer besonders bevorzugten Ausführungsform enthält die erfindungsgemäße Kautschukmischung weder Diphenylguanidin noch andere Guanidinderivate.In a particularly preferred embodiment, the rubber mixture according to the invention contains neither diphenylguanidine nor other guanidine derivatives.

Typischerweise beträgt der Gehalt an Cellulose und/oder Cellulosederivaten, worunter insbesondere Umsetzungsprodukte von Cellulose mit Phenylisocyanat, n-Buttersäureanhydrid, Essigsäureanhydrid, Butylisocyanat, Stearylchlorid, Stearylisocyanat oder Buttersäurechlorid, bevorzugt jedoch Celluoloseacetat zu verstehen ist, in den erfindungsgemäßen Kautschukmischungen bzw. Vulkanisaten ≤ 1phr, vorzugsweise < 0,5 phr, besonders bevorzugt < 0.1 phr und meist bevorzugt 0 phr.The content of cellulose and / or cellulose derivatives is typically, which includes, in particular, reaction products of cellulose with phenyl isocyanate, n-butyric anhydride, acetic anhydride, butyl isocyanate, stearyl chloride, stearyl isocyanate or butyric acid chloride, but preferably cellulose acetate, in the rubber mixtures or vulcanizates according to the invention. preferably <0.5 phr, particularly preferably <0.1 phr and most preferably 0 phr.

Die erfindungsgemäße Kautschukmischung kann sowohl in Zink-freien als auch in Zinkhaltigen Kautschukvulkanisaten vorteilhaft eingesetzt werden.The rubber mixture according to the invention can advantageously be used both in zinc-free and in zinc-containing rubber vulcanizates.

Bevorzugt wird als Verbindung der Formel (I) Triacetin verwendet.Triacetin is preferably used as the compound of formula (I).

Die erfindungsgemäße Kautschukmischung enthält von 0,1 bis 40 phr, bevorzugt von 0,2 bis 20 phr, besonders bevorzugt von 0,5 bis 15 phr, ganz besonders bevorzugt 1 bis 12 phr, weiter bevorzugt 2 bis 10 phr und meist bevorzugt 3 bis 8 phr Verbindungen der Formel (I).The rubber mixture according to the invention contains from 0.1 to 40 phr, preferably from 0.2 to 20 phr, particularly preferably from 0.5 to 15 phr, very particularly preferably 1 to 12 phr, further preferably 2 to 10 phr and most preferably 3 to 8 phr of compounds of formula (I).

Erfindungsgemäße Kautschukmischungen und erfindungsgemäße Kautschukvulkanisate können noch weitere bekannte Kautschukadditive enthalten. Die erfindungsgemäße Kautschukmischung enthält das Reversionsschutzmittel 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)-hexan ( CAS-Nr.: 151900-44-6 ).Rubber mixtures according to the invention and rubber vulcanizates according to the invention can also contain further known rubber additives. The rubber mixture according to the invention contains the anti-reversion agent 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ).

In einer bevorzugten Ausführungsform enthält die Kautschukmischung 0,1 bis 15 phr des Reversionsschutzmittels 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)hexan ( CAS-Nr. 151900-44-6 ), vorzugsweise 0,1-2 phr, besonders bevorzugt 0,2-1,0 phr.In a preferred embodiment, the rubber mixture contains 0.1 to 15 phr of the anti-reversion agent 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS number 151900-44-6 ), preferably 0.1-2 phr, particularly preferably 0.2-1.0 phr.

Bevorzugt erfolgt bei der erfindungsgemäßen Kautschukmischung die Zugabe des Additives der Formel (I) im ersten Teil des Mischprozesses bei beispielsweisen Massetemperaturen von 100 - 250 °C, sie kann jedoch auch später bei tieferen Temperaturen (40 - 100°C) beispielsweise zusammen mit Schwefel und/oder Beschleuniger erfolgen.In the case of the rubber mixture according to the invention, the additive of the formula (I) is preferably added in the first part of the mixing process at, for example, melt temperatures of 100-250 ° C., but it can also be used later at lower temperatures (40-100 ° C.), for example together with sulfur and / or accelerator.

In einer weiteren bevorzugten Form, erfolgt bei der erfindungsgemäßen Kautschukmischung die Zugabe des Additives der Formel (I) sowie die Zugabe von 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)hexan ( CAS-Nr.: 151900-44-6 ) bevorzugt im ersten Teil des Mischprozesses bei beispielsweisen Massetemperaturen von 100 - 250 °C, sie kann jedoch auch später bei tieferen Temperaturen (40 - 100°C) beispielsweise zusammen mit Schwefel und/oder Beschleuniger erfolgen.In a further preferred form, the additive of the formula (I) and the addition of 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) preferably in the first part of the mixing process at, for example, melt temperatures of 100-250 ° C, but it can also be done later at lower temperatures (40-100 ° C), for example together with sulfur and / or accelerator.

Das Additive der Formel (I) und/oder 1,6-Bis(N,N-dibenzylthiocarbamoyldithio)hexan ( CAS-Nr.: 151900-44-6 ) können unabhängig voneinander sowohl in reiner Form als auch auf einen inerten, organischen oder anorganischen Träger, vorzugsweise einen Träger ausgewählt aus der Gruppe enthaltend natürliche oder synthetische Silikate, insbesondere neutrales, acides oder basisches Silica, Aluminiumoxid, Ruß oder Zinkoxid aufgezogen und/oder daran adsorbiert eingesetzt werden.The additive of the formula (I) and / or 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) independently of one another both in pure form and on an inert, organic or inorganic support, preferably a support selected from the group comprising natural or synthetic silicates, in particular neutral, acidic or basic silica, aluminum oxide, carbon black or zinc oxide and / or attached thereto adsorbed.

Das Additiv der Formel (I) kann auch als Mischung mit 1,6-Bis(N,N-dibenzylthiocarba-moyldithio)hexan ( CAS-Nr.: 151900-44-6 ) dem Mischprozess zugegeben werden.The additive of the formula (I) can also be admixed with 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane ( CAS No .: 151900-44-6 ) be added to the mixing process.

Besonders geeignet sind die erfindungsgemäßen Kautschukmischungen für die Herstellung von Reifenlaufflächen, Subtreads, Karkassen und Apexmischungen. Reifen bzw. Reifenteile schließen dabei auch beispielsweise Laufflächen von Sommer-, Winter- und All-Seasons-Reifen sowie Laufflächen von PKW- und LKW-Reifen ein.The rubber mixtures according to the invention are particularly suitable for the production of tire treads, subtreads, carcasses and apex mixtures. Tires or tire parts also include, for example, treads from summer, winter and all-season tires, and treads from car and truck tires.

Ein weiterer Aspekt der vorliegenden Erfindung sind Vulkanisate erhältlich durch Vulkanisation der erfindungsgemäßen Kautschukmischung.Another aspect of the present invention are vulcanizates obtainable by vulcanizing the rubber mixture according to the invention.

Die hergestellten Kautschukvulkanisate eignen sich zur Herstellung diverser Kautschukprodukte, beispielsweise zur Herstellung von Reifenbauteilen insbesondere für Reifenlaufflächen, Subtreads, Karkassen, Seitenwänden, verstärkten Seitenwänden für Notlaufreifen, Apexmischungen etc. sowie für die Herstellung von technischen Gummiartikeln wie Dämpfungselementen, Walzenbelägen, Belägen von Förderbändern, Riemen, Spinnkopsen, Dichtungen, Golfballkernen, Schuhsohlen, etc.. Die erfindungsgemäßen Kautschukprodukte können insbesondere damit ausgestatteten Kraftfahrzeugen vorteilhafte Betriebseigenschaften verleihen. Daher sind solche Kraftfahrzeuge ebenfalls Gegenstand der vorliegenden Erfindung.The rubber vulcanizates produced are suitable for the manufacture of various rubber products, for example for the manufacture of tire components, in particular for tire treads, subtreads, carcasses, sidewalls, reinforced sidewalls for run-flat tires, apex mixtures, etc., and for the manufacture of technical rubber articles such as damping elements, roller coverings, coverings for conveyor belts, belts , Spinning cops, seals, golf ball cores, shoe soles, etc. The rubber products according to the invention can impart advantageous operating properties to motor vehicles equipped with them in particular. Such motor vehicles are therefore also the subject of the present invention.

Die Offenbarung umfasst weiter eine Kautschukmischung und Kautschukvulkanisat enthalten ein oder mehrere Kautschuke wie beispielsweise Naturkautschuk (NR) und/oder Synthesekautschuke. Bevorzugte Synthesekautschuke sind beispielsweise

BR
Polybutadien
ABR
Butadien/Acrylsäure-C1-C4-alkylester-Copolymerisat
CR
Polychloropren
IR
Polyisopren
SBR
Styrol/Butadien-Copolymerisate mit Styrolgehalten von 1 - 60, vorzugsweise 20-50 Gew-%
IIR
Isobutylen/Isopren-Copolymerisate
NBR
Butadien/Acrylnitril-Copolymerisate mit Acrylnitrilgehalten von 5-60, vorzugsweise 10-50 Gew.-%
HNBR
teilhydrierter oder vollständig hydrierter NBR-Kautschuk
EPDM
Ethylen/Propylen/Dien-Copolymerisate
SIBR
Styrol/Isopren-Copolymerisate
ENR
epoxidierter Naturkautschuk
The disclosure further includes a rubber mixture and rubber vulcanizate contain one or more rubbers such as natural rubber (NR) and / or synthetic rubbers. Preferred synthetic rubbers are, for example
BR
Polybutadiene
ABR
Butadiene / acrylic acid-C1-C4-alkyl ester copolymer
CR
Polychloroprene
IR
Polyisoprene
SBR
Styrene / butadiene copolymers with styrene contents of 1-60, preferably 20-50% by weight
IIR
Isobutylene / isoprene copolymers
NBR
Butadiene / acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-50% by weight
HNBR
Partially hydrogenated or fully hydrogenated NBR rubber
EPDM
Ethylene / propylene / diene copolymers
SIBR
Styrene / isoprene copolymers
ENR
epoxidized natural rubber

Die erfindungsgemäße Kautschukmischung enthält mindestens einen unpolaren Kautschuk ausgewählt aus der Gruppe bestehend aus NR, SBR, BR, IR, SIBR,IIR, ENR und EPDM, bevorzugt aus der Gruppe bestehend aus NR, SBR, BR, IR, IIR, ENR und EPDM, weiter bevorzugt aus der Gruppe bestehend aus NR, SBR, BR, IIR und EPDM, besonders bevorzugt aus der Gruppe bestehend aus NR, BR und SBR wobei der Gesamtgehalt an diesen unpolaren Kautschuken in der Kautschukmischung mindestens 50 phr, vorzugsweise mindestens 60 phr und besonders bevorzugt mindestens 70 phr beträgt, In einer besonders bevorzugten Ausführungsform beträgt der Gesamtgehalt an diesen unpolaren Kautschuken mindestens 80 phr, vorzugsweise mindestens 90 phr, weiter bevorzugt mindestens 95 phr und besonders bevorzugt mindestens 99 phr.The rubber mixture according to the invention contains at least one non-polar rubber selected from the group consisting of NR, SBR, BR, IR, SIBR, IIR, ENR and EPDM, preferably from the group consisting of NR, SBR, BR, IR, IIR, ENR and EPDM, further preferably from the group consisting of NR, SBR, BR, IIR and EPDM, particularly preferably from the group consisting of NR, BR and SBR, the total content of these nonpolar rubbers in the rubber mixture at least 50 phr, preferably at least 60 phr and particularly preferably is at least 70 phr. In a particularly preferred embodiment, the total content of these non-polar rubbers is at least 80 phr, preferably at least 90 phr, more preferably at least 95 phr and particularly preferably at least 99 phr.

Die erfindungsgemäßen Mischungen können auch polare Kautschuke beinhalten, insbesondere Kautschuke mit einem Löslichkeitsparameter von mehr als 17,6. Typischerweise ist der Gehalt an polaren Kautschuken in Form von NBR, HNBR, HXNBR und XNBR in der Kautschukmischung jeweils kleiner 10 phr, bevorzugt kleiner 1.0 phr, besonders bevorzugt kleiner 0,1 phr und ganz besonders bevorzugt kleiner 0,01 phr.The mixtures according to the invention can also contain polar rubbers, in particular rubbers with a solubility parameter of more than 17.6. The content of polar rubbers in the form of NBR, HNBR, HXNBR and XNBR in the rubber mixture is typically less than 10 phr, preferably less than 1.0 phr, particularly preferably less than 0.1 phr and very particularly preferably less than 0.01 phr.

Kieselsäure-basierender FüllstoffSilica based filler

Als kieselsäurehaltige Füllstoffe im Sinne dieser Erfindung werden folgende Stoffe verwendet:

  • Kieselsäure, insbesondere Fällungskieselsäure oder pyrogene Kieselsäure, hergestellt z.B. durch Fällung von Lösungen von Silikaten oder Flammenhydrolyse von Siliziumhalogeniden mit spezifischen Oberflächen von 5 - 1000, vorzugsweise 20 - 400 m2/g (BET-Oberffäche) und mit Primärteilchengrößen von 10 - 400 nm. Die Kieselsäuren können gegebenenfalls auch als Mischoxide mit anderen Metalloxiden wie AI-, Mg-, Ca-, Ba-, Zn-, Zr-, Ti-Oxiden vorliegen.
  • synthetische Silikate, wie Aluminiumsilikat, Erdalkalisilikate wie Magnesium- oder Calciumsilikat, mit BET-Oberflächen von 20 - 400 m2/g und Primärteilchengröße von 10 - 400 nm,
  • natürliche Silikate, wie Kaolin und andere natürliche vorkommende Kieselsäuren, sowie Mischungen dieser Stoffe.
The following substances are used as fillers containing silica in the sense of this invention:
  • Silica, in particular precipitated silica or fumed silica, produced, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surfaces of 5-1000, preferably 20-400 m 2 / g (BET surface area) and with primary particle sizes of 10-400 nm. The silicas can optionally also be present as mixed oxides with other metal oxides such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides.
  • synthetic silicates such as aluminum silicate, alkaline earth silicates such as magnesium or calcium silicate, with BET surface areas of 20-400 m 2 / g and primary particle size of 10-400 nm,
  • natural silicates, such as kaolin and other naturally occurring silicas, as well as mixtures of these substances.

Die genannten Kieselsäuren und Silikate können dabei auch in silanierter Form vorliegen, welche durch Behandlung mittels Chlorsilanen wie Monochlorsilan, Dichlorsilan, Trichlor- silan und Tetrachlorsilan, Organochlorsilanen wie Methyltrichlorsilan, Dimethyldichlorsilan, Trimethylchlorsilan, Ethyltrichlorsilan, Diethyldichlorsilan, Triethylchlorsilan sowie (Meth)acryloxy- und/oder Alkoxygruppen-haltige Silane wie Acryloxypropyltrimethoxysilan, (3-Mercaptopropyl)trimethoxysilan, 3-Glycidoxypropyltrimethoxysilan, 3-Aminopropyl- trimethoxysilan, Mono-, Di-, Tri-, oder Tetramethoxysilan erhältlich sind. Entsprechende Herstellungsverfahren sind u.a. in EP 2 033 990 B1 angegeben.The silicas and silicates mentioned can also be present in silanated form, which are obtained by treatment with chlorosilanes such as monochlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane, organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyltrichlorosilanesilane (meth) trichlorosilanesilane (meth) trichlorosilane (meth) chlorosilane (meth) trichlorosilane (meth) chlorosilane (meth) trichlorosilane and methane chlorosilane or silanes containing alkoxy groups such as acryloxypropyltrimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, mono-, di-, tri-, or tetramethoxysilane are available. Corresponding manufacturing processes are among others in EP 2 033 990 B1 specified.

Ruß-FüllstoffCarbon black filler

Zusätzlich oder alternativ zu den Kieselsäure-basierender Füllstoffen können Ruße, insbesondere sind hierfür nach dem Flammruß, Furnace- oder Gasruß-Verfahren hergestellt Ruße geeignet, welche BET-Oberflächen von 20 - 200 m<2>/g besitzen, wie SAF-, ISAF-, IISAF-, HAF-, FEF- oder GPF-Ruße eingesetzt werden.In addition or as an alternative to the silica-based fillers, carbon blacks can be used, in particular carbon blacks which have a BET surface area of 20-200 m 2 / g, such as SAF-, ISAF, are suitable for this purpose, produced using the flame black, furnace or gas black process -, IISAF, HAF, FEF or GPF carbon blacks are used.

Der Gesamtgehalt an Füllstoffen in der erfindungsgemäßen Kautschukmischung kann prinzipiell in beliebigen Grenzen variiert werden. Übliche Mengen sind 0,1 bis 200 phr, bevorzugt 30 - 150 phr. In einer bevorzugte Ausführungsform ist der Gehalt an Russ basierten Füllstoffen im Verhältnis zu Kieselsäure basierten Füllstoffen geringer.The total content of fillers in the rubber mixture according to the invention can in principle be varied within any limits. Usual amounts are 0.1 to 200 phr, preferably 30 to 150 phr. In a preferred embodiment, the content of soot-based fillers is lower than that of silica-based fillers.

Des Weiteren können erfindungsgemäße Kautschukmischungen und Kautschukvulkanisate einen oder mehrere, schwefelhaltige Silane und oder einen oder mehrere Vernetzer enthalten. Hierfür sind insbesondere Schwefel-basierende oder peroxidische Vernetzer geeignet, wobei Schwefel-basierte Vernetzer besonders bevorzugt sind.Furthermore, rubber mixtures and rubber vulcanizates according to the invention can contain one or more sulfur-containing silanes and or one or more crosslinking agents. Sulfur-based or peroxidic crosslinking agents are particularly suitable for this, with sulfur-based crosslinking agents being particularly preferred.

Generell kann der erfindungsmäßen Kautschukmischung in beliebigen Mengen sogenannter Reclaim-Rubber, wie er beispielweise in der CN101628994 beschrieben wird, eingesetzt werden.In general, the rubber mixture according to the invention can be used in any amount of so-called reclaim rubber, as is used, for example, in CN101628994 is used.

Als schwefelhaltige Silane für die erfindungsgemäße Kautschukmischung und Kautschukvulkanisate kommen bevorzugt Bis-(triethoxysilylpropyl)-tetrasulfan und das -disulfan sowie 3-(Triethoxysilyl)-1-propanthiol oder Silane wie Si 363 der Evonik, Deutschland oder Silan NXT bzw. NXT Z der Momentive (früher GE, USA), wobei der Alkoxy-Rest Methoxy oder Ethoxy bedeutet, in Einsatzmengen von 2 bis 20 Gew.-Teilen, bevorzugt 3-11 Gew.-Teilen jeweils berechnet als 100%iger Wirkstoff und bezogen auf 100 Gew.-Teile Kautschuk, in Frage. Es können aber auch Mischungen aus diesen schwefelhaltigen Silanen eingesetzt werden. Flüssige Schwefelhaltige Silane können zur besseren Dosierbarkeit und/oder Dispergierbarkeit auf einem Träger aufgezogen sein (dry liquid). Der Wirkstoffgehalt liegt vorzugsweise zwischen 30 und 70 Gew.-Teilen, bevorzugt 40 und 60 Gew.-Teilen je 100 Gew.-Teile dry liquid.Preferred sulfur-containing silanes for the rubber mixture and rubber vulcanizates according to the invention are bis (triethoxysilylpropyl) tetrasulfane and disulfane and 3- (triethoxysilyl) -1-propanethiol or silanes such as Si 363 from Evonik, Germany or Silan NXT or NXT Z from Momentive (formerly GE, USA), the alkoxy radical being methoxy or ethoxy, in amounts of 2 to 20 parts by weight, preferably 3-11 parts by weight, each calculated as a 100% active ingredient and based on 100 parts by weight. Parts of rubber, in question. Mixtures of these sulfur-containing silanes can also be used. Liquid sulfur-containing silanes can be mounted on a carrier for better meterability and / or dispersibility (dry liquid). The active substance content is preferably between 30 and 70 parts by weight, preferably 40 and 60 parts by weight per 100 parts by weight of dry liquid.

In einer bevorzugten Ausführungsform enthalten die vorliegenden Kautschukmischungen 50 bis 100 phr Kieselsäure-basierenden Füllstoff und 0,2 bis 12 phr an organischen Silanen, vorzugsweise schwefelhaltigen organischen Silanen, besonders bevorzugt Alkoxysilyl- und ganz besonders bevorzugt Trialkoxy-silylgruppen-haltigen schwefelhaltigen organischen Silanen.In a preferred embodiment, the present rubber mixtures contain 50 to 100 phr of silica-based filler and 0.2 to 12 phr of organic silanes, preferably sulfur-containing organic silanes, particularly preferably alkoxysilyl-containing and very particularly preferably trialkoxy-silyl group-containing sulfur-containing organic silanes.

Als peroxidische Vernetzer werden vorzugsweise Bis(2,4-dichlorbenzyl)peroxid, Dibenzoylperoxid, Bis(4-chlorbenzoyl)peroxid, 1,1-Bis(t-butylperoxy)-3,3,5-trimethylcylohexan, tert-Butylperbenzoat, 2,2-Bis(t-butylperoxy)butan, 4,4-Di-tert-butylperoxynonylvalerat, Dicumylperoxid, 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexan, tert-Butylcumylperoxid, 1,3-Bis(t-butylperoxyisopropyl)benzol, Di-tert-butylperoxid und 2,5-Dimethyl-2,5-di(tert-butylperoxy)-3-hexin eingesetzt.Bis (2,4-dichlorobenzyl) peroxide, dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcylohexane, tert-butyl perbenzoate, 2, 2-bis (t-butylperoxy) butane, 4,4-di-tert-butylperoxynonylvalerate, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 1,3-bis ( t-butylperoxyisopropyl) benzene, di-tert-butyl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) -3-hexyne.

Es kann vorteilhaft sein, neben diesen peroxidischen Vernetzern noch weitere Zusätze zu verwenden, mit deren Hilfe die Vernetzungsausbeute erhöht werden kann: Hierfür sind beispielsweise Triallylisocyanurat, Triallylcyanurat, Trimethylolpropantri(meth)acrylat, Triallyltrimellitat, Ethylenglycoldi(meth)acrylat, Butandioldi(meth)acrylat, Trimetylolpropan-tri(meth)acrylat, Zinkdiacrylat, Zinkdimethacrylat, 1,2-Polybutadien oder N,N'-m-Phenylen-dimaleinimid geeignet.In addition to these peroxidic crosslinking agents, it may be advantageous to use other additives with the aid of which the crosslinking yield can be increased: Examples include triallyl isocyanurate, triallyl cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate , Trimetylolpropane tri (meth) acrylate, zinc diacrylate, zinc dimethacrylate, 1,2-polybutadiene or N, N'-m-phenylene-dimaleinimide are suitable.

Als Vernetzer kann Schwefel in elementarer löslicher oder unlöslicher Form oder in Form von Schwefelspendern eingesetzt werden. Als Schwefelspender kommen beispielsweise Dimorpholyldisulfid (DTDM), 2-Morpholinodithiobenzothiazol (MBSS), Caprolactamdisulfid, Dipentamethylenthiuramtetrasulfid (DPTT), Tetramethylthiuramdisulfid (TMTD) und Tetrabenzylthiuramdisulfid (TBzTD) in Frage. In einer bevorzugten Ausführungsform enthält die Kautschukmischung 0,1-15 phr TBzTD, vorzugsweise 0,1-2 phr, besonders bevorzugt 0,1-0,5 phr.Sulfur can be used as a crosslinker in elemental soluble or insoluble form or in the form of sulfur donors. Examples of sulfur donors are dimorpholyl disulfide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulfide, dipentamethylene thiuram tetrasulfide (DPTT), tetramethylthiuram disulfide (TMTD) and tetrabenzylthiuram disulfide (TBzTD). In a preferred embodiment, the rubber mixture contains 0.1-15 phr TBzTD, preferably 0.1-2 phr, particularly preferably 0.1-0.5 phr.

Grundsätzlich kann die Vernetzung der erfindungsgemäßen Kautschukmischung mit Schwefel oder Schwefelspendern allein erfolgen, oder zusammen mit Vulkanisationsbeschleunigern, wofür z.B. Dithiocarbamate, Thiurame, Thiazole, Sulfenamide, Xanthogenate, bi- oder polycyclische Amine, Dithiophosphate, Caprolactame und Thioharnstoffderivate geeignet sind. Weiterhin sind auch Zink-diamindiisocyanat, Hexamethylentetramin, 1,3-Bis(citraconimidomethyl)benzol sowie zyklische Disulfane geeignet. Bevorzugt enthalten die erfindungsgemäßen Kautschukmischungen Schwefel-basierende Vernetzer und Vulkanisationsbeschleuniger.In principle, the rubber mixture according to the invention can be crosslinked with sulfur or sulfur donors alone, or together with vulcanization accelerators, for which purpose e.g. Dithiocarbamates, thiurams, thiazoles, sulfenamides, xanthates, bi- or polycyclic amines, dithiophosphates, caprolactams and thiourea derivatives are suitable. Zinc-diamine diisocyanate, hexamethylenetetramine, 1,3-bis (citraconimidomethyl) benzene and cyclic disulfanes are also suitable. The rubber mixtures according to the invention preferably contain sulfur-based crosslinking agents and vulcanization accelerators.

Besonders bevorzugt werden als Vernetzungsmittel Schwefel, Magnesiumoxid und/oder Zinkoxid eingesetzt, denen die bekannten Vulkanisationsbeschleuniger, wie Merkaptobenzothiazole, Thiazolsulfenamide, Thiurame, Thiocarbamate, Xanthogenate und Thiophosphate zugesetzt werden.Sulfur, magnesium oxide and / or zinc oxide, to which the known vulcanization accelerators such as mercaptobenzothiazoles, thiazole sulfenamides, thiurams, thiocarbamates, xanthates and thiophosphates are added, are particularly preferably used as crosslinking agents.

Die Vernetzungsmittel und Vulkanisationsbeschleuniger werden bevorzugt in Mengen von 0,1 bis 10 phr, besonders bevorzugt von 0,1 bis 5 phr, in die erfindungsgemäßen Kautschukmischung eingesetzt.The crosslinking agents and vulcanization accelerators are preferably used in amounts of 0.1 to 10 phr, particularly preferably 0.1 to 5 phr, in the rubber mixture according to the invention.

Die erfindungsgemäße Kautschukmischung und das erfindungsgemäße Kautschukvulkansiat können weitere Kautschukhilfsmittel enthalten, wie beispielsweise Haftsysteme, Alterungsschutzmittel, Wärmestabilisatoren, Lichtschutzmittel, Antioxidantien, insbesondere Ozonschutzmittel, Flammschutzmittel, Verarbeitungshilfsmittel, Schlagzähfestigkeitsverbesserer, Weichmacher, Tackifier, Treibmittel, Farbstoffe, Pigmente, Wachse, Streckmittel, organische Säuren, Verzögerer, Metalloxide und Aktivatoren, insbesondere Triethanolamin, Polyethylenglykol, Hexantriol und Reversionsschutzmittel.The rubber mixture according to the invention and the vulcanized rubber according to the invention can contain further rubber auxiliaries, such as, for example, adhesion systems, anti-aging agents, heat stabilizers, light stabilizers, antioxidants, in particular ozone protection agents, flame retardants, processing aids, impact strength improvers, Plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators, in particular triethanolamine, polyethylene glycol, hexanetriol and anti-reversion agents.

Diese Kautschukhilfsmittel werden in üblichen Mengen eingesetzt, die sich u. a. nach dem Verwendungszweck der Vulkanisate richten. Übliche Mengen sind 0,1 bis 30 phr.These rubber auxiliaries are used in conventional amounts, which u. a. according to the intended use of the vulcanizates. Usual amounts are 0.1 to 30 phr.

Als Alterungsschutzmittel werden bevorzugt alkylierte Phenole, styrolisiertes Phenol, sterisch gehinderte Phenole wie 2,6-Di-tert.-butylphenol, 2,6-Di-tert-butyl-p-kresol (BHT), 2,6-Di-tert.-butyl-4-ethylphenol, estergruppenhaltige sterisch gehinderte Phenole, thioetherhaltige sterisch gehinderte Phenole, 2,2'-Methylen-bis-(4-methyl-6-tert-butylphenol) (BPH) sowie sterisch gehinderte Thiobisphenole verwendet.Preferred anti-aging agents are alkylated phenols, styrenated phenol, sterically hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert. -butyl-4-ethylphenol, sterically hindered phenols containing ester groups, thioether-containing sterically hindered phenols, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) (BPH) and sterically hindered thiobisphenols.

Falls eine Verfärbung des Kautschuks ohne Bedeutung ist, können auch aminische Alterungsschutzmittel z.B. Mischungen aus Diaryl-p-phenylendiaminen (DTPD), octyliertes Diphenylamin (ODPA), Phenyl-α-naphthylamin (PAN), Phenyl-β-naphthylamin (PBN), vorzugsweise solche auf Phenylendiaminbasis, z. B. N-Isopropyl-N'-phenyl-p-phenylendiamin, N-1,3-Dimethylbutyl-N'-Phenyl-p-phenylendiamin (6PPD), N-1,4-Dimethylpentyl-N'-phenyl-p-phenylendiamin (7PPD), N,N'-bis-(1,4-Dimethylpentyl)-p-phenylendiamin (77PD) eingesetzt werden.If discoloration of the rubber is of no importance, amine anti-aging agents, e.g. Mixtures of diaryl-p-phenylenediamines (DTPD), octylated diphenylamine (ODPA), phenyl-α-naphthylamine (PAN), phenyl-β-naphthylamine (PBN), preferably those based on phenylenediamine, e.g. B. N-isopropyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p- phenylene diamine (7PPD), N, N'-bis (1,4-dimethylpentyl) -p-phenylene diamine (77PD) can be used.

Weitere Alterungsschutzmittel sind Phosphite wie Tris-(nonylphenyl)phosphit, polymerisiertes 2,2,4-Trimethyl-1,2-dihydrochinolin (TMQ), 2-Mercaptobenzimidazol (MBI), Methyl-2-Mercaptobenzimidazol (MMBI), Zinkmethylmercaptobenzimidazol (ZMMBI), welche meist in Kombination mit obigen phenolischen Alterungsschutzmitteln eingesetzt werden. TMQ, MBI und MMBI werden vor allem für NBR-Kautschuke verwendet, welche peroxidisch vulkanisiert werden.Other anti-aging agents are phosphites such as tris (nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), 2-mercaptobenzimidazole (MBI), methyl-2-mercaptobenzimidazole (MMBI), zinc methyl mercaptobenzimidazole (ZMMBI) , which are mostly used in combination with the above phenolic anti-aging agents. TMQ, MBI and MMBI are mainly used for NBR rubbers, which are vulcanized peroxidically.

Die Ozonbeständigkeit kann durch Antioxidantien wie beispielsweise N-1,3-Dimethylbutyl-N'-phenyl-p-phenylendiamin (6PPD), N-1,4-Dimethylpentyl-N'-phenyl-p-phenylendiamin (7PPD), N,N'-Bis- (1,4-dimethylpentyl)-p-phenylendiamin (77PD), Enolether oder cyclische Acetale verbessert werden.The ozone resistance can be improved by antioxidants such as N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine (7PPD), N, N '-Bis- (1,4-dimethylpentyl) -p-phenylenediamine (77PD), enol ethers or cyclic acetals can be improved.

Verarbeitungshilfsmittel sollen zwischen den Kautschuk-Partikeln wirksam werden und Reibungskräften beim Mischen, Plastifizieren und Verformen entgegenwirken. Als Verarbeitungshilfsmittel können die erfindungsgemäßen Kautschukmischungen alle für die Verarbeitung von Kunststoffen üblichen Gleitmittel enthalten, wie beispielsweise Kohlenwasserstoffe, wie Öle, Paraffine und PE-Wachse, Fettalkohole mit 6 bis 20 C-Atomen, Ketone, Carbonsäuren, wie Fettsäuren und Montansäuren, oxidiertes PE-Wachs, Metallsalze von Carbonsäuren, Carbonsäureamide sowie Carbonsäureester, beispielsweise mit den Alkoholen Ethanol, Fettalkoholen, Glycerin, Ethandiol, Pentaerythrit und langkettigen Carbonsäuren als Säurekomponente.Processing aids should act between the rubber particles and counteract frictional forces during mixing, plasticizing and shaping. As a processing aid, the rubber mixtures according to the invention can contain all lubricants customary for the processing of plastics, such as, for example, hydrocarbons, such as oils, paraffins and PE waxes, fatty alcohols with 6 to 20 carbon atoms, Ketones, carboxylic acids such as fatty acids and montanic acids, oxidized PE wax, metal salts of carboxylic acids, carboxylic acid amides and carboxylic acid esters, for example with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as the acid component.

Um die Entflammbarkeit zu vermindern und die Rauchentwicklung beim Verbrennen zu verringern, kann die erfindungsgemäße Kautschukmischungszusammensetzung auch Flammschutzmittel enthalten. Hierfür werden beispielsweise Antimontrioxid, Phosphorsäureester, Chlorparaffin, Aluminiumhydroxid, Borverbindungen, Zinkverbindungen, Molybdäntrioxid, Ferrocen, Calciumcarbonat oder Magnesiumcarbonat verwendet.In order to reduce the flammability and to reduce the smoke development when burning, the rubber mixture composition according to the invention can also contain flame retardants. Antimony trioxide, phosphoric acid esters, chlorinated paraffin, aluminum hydroxide, boron compounds, zinc compounds, molybdenum trioxide, ferrocene, calcium carbonate or magnesium carbonate are used for this purpose.

Vor der Vernetzung können der erfindungsgemäßen Kautschukmischung und dem erfindungsgemäßen Kautschukvulkanisat auch weitere Kunststoffe beigefügt werden, welche beispielsweise als polymere Verarbeitungshilfsmittel oder Schlagzähigkeitsverbesserer wirken. Diese Kunststoffe werden bevorzugt gewählt aus der Gruppe bestehend aus den Homo- und Copolymeren auf Basis von Ethylen, Propylen, Butadien, Styrol, Vinylacetat, Vinylchlorid, Glycidylacrylat, Glycidylmethacrylat, Acrylaten und Methacrylaten mit Alkoholkomponenten von verzweigten oder unverzweigten C1- bis C10-Alkoholen, wobei Polyacrylate mit gleichen oder verschiedenen Alkoholresten aus der Gruppe der C4- bis C8-Alkohole, insbesondere des Butanols, Hexanols, Octanols und 2-Ethylhexanols, Polymethylmethacrylat, Methylmethacrylat-Butylacrylat-Copolymere, Methylmethacrylat-Butylmethacrylat-Copolymere, Ethylen-Vinylacetat-Copolymere, chloriertes Polyethylen, Ethylen-Propylen-Copolymere, Ethylen-Propylen-Dien-Copolymere besonders bevorzugt sind.Before the crosslinking, the rubber mixture according to the invention and the rubber vulcanizate according to the invention can also be admixed with further plastics which act, for example, as polymeric processing aids or impact modifiers. These plastics are preferably selected from the group consisting of the homopolymers and copolymers based on ethylene, propylene, butadiene, styrene, vinyl acetate, vinyl chloride, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched or unbranched C1 to C10 alcohols, where polyacrylates with the same or different alcohol residues from the group of the C4 to C8 alcohols, in particular butanol, hexanol, octanol and 2-ethylhexanol, polymethyl methacrylate, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, ethylene-vinyl acetate copolymers, chlorinated polyethylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers are particularly preferred.

Bekannte Haftsysteme basieren auf Resorcin, Formaldehyd und Silica, die sogenannten RFS- Direkthaftsysteme. Diese Direkthaftsysteme können in beliebiger Menge der erfindungsgemäßen Kautschukmischung, zu jedem Zeitpunkt des Einmischens in die erfindungsgemäße Kautschukmischung, eingesetzt werden.Known adhesive systems are based on resorcinol, formaldehyde and silica, the so-called RFS direct adhesive systems. These direct adhesion systems can be used in any amount of the rubber mixture according to the invention, at any time when it is mixed into the rubber mixture according to the invention.

Als Formaldehyd-Spender eignen sich neben Hexamethylentetramin auch Methylolaminderivate. Eine mögliche Haftverbesserung wird durch Zugabe von zur Kunstharzbildung befähigten Komponenten wie Phenol und oder Amine und Aldehyde oder Aldehyde abspaltende Verbindungen zu den bekannten Kautschukmischungen erzielt. Eine breite Anwendung als Harzbildungskomponenten in Kautschukhaftmischungen finden Resorzin und Hexamethylentetramin (HEXA) ( GB-PS 801 928 , FR-PS 1 021 959 ), gegebenenfalls in Kombination mit Kieselsäurefüllstoff ( DE-AS 1 078 320 ).In addition to hexamethylenetetramine, methylolamine derivatives are also suitable as formaldehyde donors. A possible improvement in adhesion is achieved by adding components capable of forming synthetic resins, such as phenol and / or amines and aldehydes or aldehydes or compounds which split off the known rubber mixtures. Resorzine and hexamethylenetetramine (HEXA) (are widely used as resin-forming components in rubber adhesive mixtures GB-PS 801 928 , FR-PS 1 021 959 ), optionally in combination with silica filler ( DE-AS 1 078 320 ).

Das erfindungsgemäße Kautschukvulkanisat kann beispielsweise zur Herstellung von Schaumstoffen verwendet werden. Dazu werden ihr chemisch oder physikalisch wirkende Treibmittel zugefügt. Als chemisch wirkende Treibmittel kommen alle für diesen Zweck bekannten Substanzen in Betracht, wie beispielsweise Azodicarbonamid, p-Toluolsulfonylhydrazid, 4,4'-Oxybis(benzolsulfohydrazid), p-Toluolsulfonylsemicarbazid, 5-Phenyltetrazol, N,N'-Dinitroso-pentamethylentetramin, Zinkcarbonat oder Natriumhydrogencarbonat sowie diese Substanzen enthaltende Mischungen. Als physikalisch wirkende Treibmittel sind beispielsweise Kohlendioxid oder Halogenkohlenwasserstoffe geeignet.The rubber vulcanizate according to the invention can be used, for example, for the production of foams. For this, chemical or physical blowing agents are added. Suitable chemical blowing agents are all substances known for this purpose, such as, for example, azodicarbonamide, p-toluenesulfonylhydrazide, 4,4'-oxybis (benzenesulfohydrazide), p-toluenesulfonylsemicarbazide, 5-phenyltetrazole, N, N'-dinitrosopentamethylenetetramine, zinc carbonate or sodium hydrogen carbonate and mixtures containing these substances. Carbon dioxide or halogenated hydrocarbons, for example, are suitable as physically active blowing agents.

Die Vulkanisation der erfindungsgemäßen Kautschukmischungen erfolgt typischerweise bei Temperaturen von 100 - 250 °C, vorzugsweise 130 - 180 °C, wobei gegebenenfalls ein Druck von 10 - 200 bar vorherrscht.The rubber mixtures according to the invention are typically vulcanized at temperatures of 100-250 ° C., preferably 130-180 ° C., a pressure of 10-200 bar possibly prevailing.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von Verbindungen der Formel (I) zur Herstellung der erfindungsgemäßen Kautschukmischungen, Vulkanisate und/oder Kautschukprodukte.The present invention furthermore relates to the use of compounds of the formula (I) for the preparation of the rubber mixtures, vulcanizates and / or rubber products according to the invention.

BeispieleExamples

Die Herstellung der erfindungsgemäßen Kautschukvulkanisate kann beispielsweise in folgenden Mischstufen erfolgen:The rubber vulcanizates according to the invention can be produced, for example, in the following mixing stages:

1. Mischstufe:1st mixing stage:

  • ▪ Kautschuk (z.B. Mischung aus SBR und BR) werden in einem Innenmischer vorgelegt und ca. 30 Sekunden gemischt▪ Rubber (e.g. mixture of SBR and BR) are placed in an internal mixer and mixed for approx. 30 seconds
  • ▪ Gegebenenfalls Zugabe von hydroxylgruppenhaltigem oxidischem Füllstoff und Silan zur Oberflächenmodifizierung (z.B. Zugabe von zwei Drittel Kieselsäure, zwei Drittel Silan, mischen für ca. 60 Sekunden und weitere Zugabe von ein Drittel Kieselsäure, ein Drittel Silan, mischen für ca. 60 Sekunden)▪ If necessary, addition of hydroxyl group-containing oxidic filler and silane for surface modification (e.g. addition of two thirds silica, two thirds silane, mix for approx. 60 seconds and further addition of one third silica, one third silane, mix for approx. 60 seconds)
  • ▪ Zugabe des Additivs der Formel (I) und gegebenenfalls Zugabe von Ruß, Öl, Alterungsschutzmitteln, Zinkoxid sowie Ozonschutzwachse, mischen für ca. 60 Sekunden.▪ Add the additive of formula (I) and, if necessary, add carbon black, oil, anti-aging agents, zinc oxide and anti-ozone wax, mix for approx. 60 seconds.

Dieser Mischungsvorgang kann bei Temperaturen von 100 bis 170°C erfolgen, vorzugsweise im Bereich von 150°C.This mixing process can take place at temperatures of 100 to 170 ° C, preferably in the range of 150 ° C.

2. Mischstufe:2nd mixing stage:

Nach Abschluss der ersten Mischstufe wird das Mischstück von einem nachgeschalteten Walzwerk aufgenommen und zu einer Platte, einem Streifen oder Pellets ausgeformt und für 24 Stunden bei Raumtemperatur gelagert.After completion of the first mixing stage, the mixing piece is taken up by a downstream rolling mill and shaped into a plate, a strip or pellets and stored for 24 hours at room temperature.

Verarbeitungstemperaturen liegen hierbei unter 60°C.Processing temperatures are below 60 ° C.

3. Mischstufe:3rd mixing stage:

In der dritten Mischstufe erfolgt ein Nachzwicken bei 140 bis 170°C, vorzugsweise bei 150°C zum Beispiel in einem Kneter /Innenmischer.In the third mixing stage, pinching is carried out at 140 to 170 ° C., preferably at 150 ° C., for example in a kneader / internal mixer.

4. Mischstufe:4th mixing stage:

Zugabe von Zusatzstoffen wie zum Beispiel Vulkanisationsbeschleuniger und/oder Schwefel-Vernetzer, vorzugsweise auf einer Walze bei niedrigen Temperaturen (< 80°C).Addition of additives such as vulcanization accelerators and / or sulfur crosslinkers, preferably on a roller at low temperatures (<80 ° C).

Geeignete Aggregate für die Mischungsherstellung sind an sich bekannt und schließen beispielsweise Walzen, Innenmischer oder auch Mischextruder ein.Suitable units for the production of mixtures are known per se and include, for example, rollers, internal mixers or also mixing extruders.

Herstellung der erfindungsgemäßen KautschukvulkanisateProduction of the rubber vulcanizates according to the invention

Aus den in Tabelle 1 aufgeführten Kautschuk-Rezepturen für die Beispiele 1 und 2 sowie für die Referenzbeispiele wurden Vulkanisate hergestellt. Dazu wurden jeweils in einem mehrstufigen Mischprozess, wie unten beschrieben, die jeweiligen Bestandteile der Beispiele 1 und 2 sowie der Referenzbeispiele gemischt und die Mischungen anschließend bei 170°C ausvulkanisiert.Vulcanizates were produced from the rubber formulations listed in Table 1 for Examples 1 and 2 and for the reference examples. For this purpose, the respective constituents of Examples 1 and 2 and of the reference examples were mixed in a multi-stage mixing process, as described below, and the mixtures were then vulcanized at 170 ° C.

1. Mischstufe:1st mixing stage:

  • ▪ BUNA® CB 24 und BUNA® VSL 5025-2 wurde in einem Innenmischer vorgelegt und ca. 30 Sekunden gemischt▪ BUNA® CB 24 and BUNA® VSL 5025-2 were placed in an internal mixer and mixed for approx. 30 seconds
  • ▪ Zugabe zwei Drittel VULKASIL® S, zwei Drittel SI® 69, zwei Drittel Additiv der Formel (I) mischen für ca. 60 Sekunden▪ Add two thirds VULKASIL® S, two thirds SI® 69, two thirds additive of formula (I) mix for approx. 60 seconds
  • ▪ Zugabe ein Drittel VULKASIL® S, ein Drittel SI® 69, ein Drittel Additiv der Formel (I) sowie TUDALEN 1849-TE, mischen ca. 60 Sekunden▪ Add a third VULKASIL® S, a third SI® 69, a third additive of formula (I) and TUDALEN 1849-TE, mix for approx. 60 seconds

Zugabe von CORAX® N 339, EDENOR® C 18 98-100, VULKANOX® 4020/LG, VULKANOX® HS/LG, ZINKWEISS ROTSIEGEL sowie ANTILUX® 654, mischen für ca. 60 SekundenAdd CORAX® N 339, EDENOR® C 18 98-100, VULKANOX® 4020 / LG, VULKANOX® HS / LG, ZINKWEISS RED SEAL and ANTILUX® 654, mix for approx. 60 seconds

Dieser Mischungsvorgang erfolgte bei einer Temperatur von 150°C.This mixing process was carried out at a temperature of 150 ° C.

2. Mischstufe:2nd mixing stage:

Nach Abschluss der ersten Mischstufe wurde das Mischstück von einem nachgeschalteten Walzwerk aufgenommen und zu einer Platte ausgeformt und für 24 Stunden bei Raumtemperatur gelagert.After completion of the first mixing stage, the mixing piece was taken up by a downstream rolling mill and formed into a plate and stored for 24 hours at room temperature.

Verarbeitungstemperaturen liegen hierbei unter 60°C.Processing temperatures are below 60 ° C.

3. Mischstufe:3rd mixing stage:

In der dritten Mischstufe erfolgte ein Nachzwicken bei 150°C in einem Kneter.In the third mixing stage, a pinch was carried out at 150 ° C. in a kneader.

4. Mischstufe:4th mixing stage:

Zugabe der Zusatzstoffe MAHLSCHWEFEL 90/95 CHANCEL, VULKACIT® CZ/C, RHENOGRAN® DPG-80 auf einer Walze bei Temperaturen unter 80°C.Add the additives MAHLSCHWEFEL 90/95 CHANCEL, VULKACIT® CZ / C, RHENOGRAN® DPG-80 on a roller at temperatures below 80 ° C.

Die hergestellten Kautschukmischungen und Vulkanisate wurden den unten angegebenen technischen Prüfungen unterzogen. Die ermittelten Werte sind ebenfalls Tabelle 2 zu entnehmen.The rubber compounds and vulcanizates produced were subjected to the technical tests specified below. The values determined are also shown in Table 2.

Bestimmung der Eigenschaften von Kautschukmischung bzw. Vulkanisaten:Determination of the properties of rubber compounds or vulcanizates: Mooney-Viskositätsmessung:Mooney viscosity measurement:

Die Bestimmung erfolgte mittels Scherscheibenviskosimeter gemäß ASTM D 1646. Die Viskosität lässt sich aus der Kraft, die Kautschuke (und Kautschukmischungen) ihrer Verarbeitung entgegensetzen, direkt bestimmen. Beim Scherscheibenviskosimeter nach Mooney wird eine geriffelte Scheibe oben und unten mit Probensubstanz umschlossen und in einer beheizbaren Kammer mit etwa zwei Umdrehungen in der Minute bewegt. Die hierzu erforderliche Kraft wird als Drehmoment gemessen und entspricht der jeweiligen Viskosität. Die Probe wird in der Regel eine Minute lang auf 100°C vorgewärmt; die Messung dauert weitere 4 Minuten, wobei die Temperatur konstant gehalten wird. Die Viskosität wird zusammen mit den jeweiligen Prüfbedingungen angegeben, beispielsweise ML (1+4) 100°C (Mooney viscosity, large rotor, Vorwärmzeit und Prüfzeit in Minuten, Prüftemperatur).The determination was carried out using a shear disk viscometer in accordance with ASTM D 1646. The viscosity can be determined directly from the force that rubbers (and rubber mixtures) oppose to their processing. In the Mooney shear disk viscometer, a corrugated disk is enclosed at the top and bottom with sample substance and moved in a heatable chamber at about two revolutions per minute. The force required for this is measured as torque and corresponds to the respective viscosity. The sample is usually preheated to 100 ° C for one minute; the measurement takes another 4 minutes, keeping the temperature constant. The viscosity is specified together with the respective test conditions, for example ML (1 + 4) 100 ° C (Mooney viscosity, large rotor, preheating time and test time in minutes, test temperature).

Scorch-Verhalten (t 5):Scorch behavior (t 5):

Des Weiteren kann mit der gleichen Prüfung wie oben beschrieben auch das Scorch-Verhalten einer Mischung gemessen werden. Die gewählte Temperatur betrug 130°C. Der Rotor läuft solang, bis der Drehmomentwert nach Durchlaufen eines Minimums auf 5 Mooney-Einheiten relativ zum Minimumwert angestiegen ist (t5). Je größer der Wert ist (Einheit Sekunden), umso langsamer findet die Anvulkanisation statt und umso höher ist die Verarbeitungssicherheit.Furthermore, the scorch behavior of a mixture can be measured with the same test as described above. The selected temperature was 130 ° C. The rotor runs until the torque value has risen to 5 Mooney units relative to the minimum value after passing through a minimum (t5). The larger the value (unit seconds), the slower the vulcanization takes place and the higher the processing security.

Rheometer (Vulkameter) Ausvulkanisationszeit 170°C (t95):Rheometer (vulkameter) curing time 170 ° C (t95):

Der Vulkanisationsverlauf am MDR (moving die rheometer) und dessen analytischen Daten werden an einem Monsanto-Rheometer MDR 2000 nach ASTM D5289-95 gemessen. Als Ausvulkanisationszeit, wird die Zeit bestimmt, bei der 95% des Kautschuks vernetzt ist. Die gewählte Temperatur betrug 170°C.The course of vulcanization on the MDR (moving the rheometer) and its analytical data are measured on a Monsanto rheometer MDR 2000 in accordance with ASTM D5289-95. The time at which 95% of the rubber is crosslinked is determined as the vulcanization time. The selected temperature was 170 ° C.

Bestimmung der Härte:Determination of hardness:

Zur Bestimmung der Härte der erfindungsgemäßen Kautschukmischung wurden 6 mm starke Walzfelle aus der Kautschukmischung gemäß Rezepturen der Tabelle 1 hergestellt. Aus den Walzfellen wurden Prüfkörper mit 35 mm Durchmesser geschnitten, deren Shore-Härte A mittels eines digitalen Shore-Härte-Testers (Zwick GmbH & Co. KG, Ulm) bestimmt wurden. Die Härte eines Kautschukvulkanisats gibt einen ersten Hinweis über dessen Steifigkeit wieder.To determine the hardness of the rubber mixture according to the invention, 6 mm thick rolled skins were made from the rubber mixture in accordance with the recipes in Table 1 produced. Test specimens with a diameter of 35 mm were cut from the rolled skins and their Shore hardness A was determined using a digital Shore hardness tester (Zwick GmbH & Co. KG, Ulm). The hardness of a rubber vulcanizate gives a first indication of its rigidity.

Dyn. Dämpfung:Dynamic damping:

Dynamische Prüfverfahren werden zur Charakterisierung des Verformungsverhaltens von Elastomeren unter periodisch veränderten Belastungen verwendet. Eine von außen angebrachte Spannung verändert die Konformation der Polymerkette.Dynamic test methods are used to characterize the deformation behavior of elastomers under periodically changing loads. External tension changes the conformation of the polymer chain.

Bei dieser Messung wird der Verlustfaktor tan delta indirekt über das Verhältnis zwischen Verlustmodul G" und Speichermodul G' bestimmt. Tabelle 1: Kautschuk-Rezeptur Im Folgenden soll die vorliegende Erfindung durch Beispiele erläutert werden ohne diese jedoch darauf zu beschränken. Bestandteile der erfindungsgemäßen Kautschukzubereitungen: Kautschuk-rezeptur Referenz 1 Kautschuk-rezeptur Referenz 2 Kautschuk-rezeptur Beispiel 1 Kautschuk-rezeptur Beispiel 2 Kautschuk-rezeptur Referenz 3 BUNA CB 24 30 30 30 30 30 BUNA VSL 5025-2 96 96 96 96 96 CORAX N 339 6,4 6,4 6,4 6,4 6,4 VULKASIL S 80 80 80 80 80 TUDALEN 1849-TE 8 8 8 8 8 EDENOR C 18 98-100 1 1 1 1 1 VULKANOX 4020/LG 1 1 1 1 1 VULKANOX HS/LG 1 1 1 1 1 ZINKWEISS ROTSIEGEL 2,5 2,5 2,5 2,5 2,5 ANTILUX 654 1,5 1,5 1,5 1,5 1,5 SI 69 6,4 6,4 6,4 6,4 6,4 VULKACIT CZ/C 1,5 1,5 1,5 1,5 1,5 Mahlschwefel 90/95 Chancel 1,5 1,5 1,5 1,5 1,5 Vulcuren - 0,4 0,4 0,4 - RHENOGRAN DPG-80 2,5 - - - - Triacetin (Additiv der Formel (I)) - - 2 8 8 Mengenangaben in phr (Gewichtsteile pro 100 Teile Kautschuk) Handelsname Erläuterung Hersteller/Vertrieb BUNA CB 24 BR Lanxess Deutschland GmbH BUNA VSL 5025-2 SBR Lanxess Deutschland GmbH CORAX N 339 Ruß Degussa-Evonik GmbH VULKASIL S Kieselsäure Lanxess Deutschland GmbH RHENOGRAN DPG-80 Diphenylguanidin RheinChemie TUDALEN 1849-TE Mineralöl Hansen&Rosenthal KG EDENOR C 18 98-100 Stearinsäure Cognis Deutschland GmbH VULKANOX 4020/LG N-1,3-Dimethylbutyl-N-phenyl-p-phenylendiamin Lanxess Deutschland GmbH VULKANOX HS/LG 2,2,4-Trimethyl-1,2-dihydrochinolin polymerisiert Lanxess Deutschland GmbH ZINKWEISS ROTSIEGEL Zinkoxid Grillo Zinkoxid GmbH ANTILUX 654 Lichtschutzwachs RheinChemie Rheinau GmbH SI 69 Bis(triethoxysilylpropyl)tetrasulfid Evonik Industries VULKACIT CZ/C N-cyclohexyl-2-benzothiazol-sulfenamid Lanxess Deutschland GmbH Vulcuren 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)-hexane Lanxess Deutschland GmbH Triacetin Glycerintriacetat Lanxess Deutschland GmbH MAHLSCHWEFEL 90/95 CHANCEL Schwefel Solvay Deutschland GmbH Tabelle 2: Zusammenstellung der Ergebnisse Kautschuk-rezeptur Referenz 1 Kautschuk-rezeptur Referenz 2 Kautschuk-rezeptur Beispiel 1 Kautschuk-rezeptur Beispiel 2 Kautschuk-rezeptur Referenz 3 ML 1+4 (Mooney Viskosität) ME 87 92 89 81 81 MS-t5 (Scorch-Zeit) sec 1344 1435 1588 2036 2998 Ausvulkanisationszeit (t95) s 1253 1167 1405 1554 2030 Härte Mittelwert Shore A 70 70 70 72 68 Bruchdehnung % 351 365 359 358 400 Zugfestig keit MPa 18,9 19,8 20,0 18,8 18,8 Abrieb DIN 53516 mm3 67 60 54 53 44 Verlustfaktor tan d (60°C) 0,134 0,123 0,130 0,122 0,137 In this measurement, the loss factor tan delta is determined indirectly via the relationship between loss module G "and storage module G '. <b> Table 1: Rubber formulation </b> In the following, the present invention is to be explained by examples, but without restricting it thereto. Components of the rubber preparations according to the invention: Rubber formulation reference 1 Rubber formulation reference 2 Rubber formulation example 1 Rubber formulation example 2 Rubber formulation reference 3 BUNA CB 24 30th 30th 30th 30th 30th BUNA VSL 5025-2 96 96 96 96 96 CORAX N 339 6.4 6.4 6.4 6.4 6.4 VULKASIL S 80 80 80 80 80 TUDALEN 1849-TE 8th 8th 8th 8th 8th EDENOR C 18 98-100 1 1 1 1 1 VULKANOX 4020 / LG 1 1 1 1 1 VULKANOX HS / LG 1 1 1 1 1 ZINC WHITE RED SEAL 2.5 2.5 2.5 2.5 2.5 ANTILUX 654 1.5 1.5 1.5 1.5 1.5 SI 69 6.4 6.4 6.4 6.4 6.4 VULKACIT CZ / C 1.5 1.5 1.5 1.5 1.5 Grinding sulfur 90/95 Chancel 1.5 1.5 1.5 1.5 1.5 Vulcures - 0.4 0.4 0.4 - RHENOGRAN DPG-80 2.5 - - - - Triacetin (additive of formula (I)) - - 2nd 8th 8th Quantities in phr (parts by weight per 100 parts of rubber) Trade name Explanation Manufacturer / sales BUNA CB 24 BR Lanxess Germany GmbH BUNA VSL 5025-2 SBR Lanxess Germany GmbH CORAX N 339 soot Degussa-Evonik GmbH VULKASIL S Silica Lanxess Germany GmbH RHENOGRAN DPG-80 Diphenylguanidine RheinChemie TUDALEN 1849-TE mineral oil Hansen & Rosenthal KG EDENOR C 18 98-100 Stearic acid Cognis Germany GmbH VULKANOX 4020 / LG N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine Lanxess Germany GmbH VULKANOX HS / LG 2,2,4-Trimethyl-1,2-dihydroquinoline polymerized Lanxess Germany GmbH ZINC WHITE RED SEAL zinc oxide Grillo Zinkoxid GmbH ANTILUX 654 Sunscreen wax RheinChemie Rheinau GmbH SI 69 Bis (triethoxysilylpropyl) tetrasulfide Evonik Industries VULKACIT CZ / C N-cyclohexyl-2-benzothiazole sulfenamide Lanxess Germany GmbH Vulcures 1,6-bis (N, N'-dibenzylthiocarbamoyldithio) hexanes Lanxess Germany GmbH Triacetin Glycerol triacetate Lanxess Germany GmbH GRIND SULFUR 90/95 CHANCEL sulfur Solvay Germany GmbH Rubber formulation reference 1 Rubber formulation reference 2 Rubber formulation example 1 Rubber formulation example 2 Rubber formulation reference 3 ML 1 + 4 (Mooney viscosity) ME 87 92 89 81 81 MS-t5 (scorch time) sec 1344 1435 1588 2036 2998 Curing time (t95) s 1253 1167 1405 1554 2030 Hardness mean Shore A 70 70 70 72 68 Elongation at break % 351 365 359 358 400 Tensile strenght MPa 18.9 19.8 20.0 18.8 18.8 Abrasion DIN 53516 mm 3 67 60 54 53 44 Dissipation factor tan d (60 ° C) 0.134 0.123 0.130 0.122 0.137

Überraschend wurde nun gefunden, dass die erfindungsgemäßen Kautschukmischungen deutlich längere Scorchzeiten (MS-t5) und niedrige Mooney Viskositäten aufweisen und die daraus erhaltenen Vulkanisate exzellente Abriebwerte, sowie eine hohe Shore A Härte, Zugfestigkeit, Bruchdehnung und niedrige tan d-Werte (60°C) zeigenSurprisingly, it has now been found that the rubber mixtures according to the invention have significantly longer scorch times (MS-t5) and low Mooney viscosities and that the vulcanizates obtained from them have excellent abrasion values, as well as high Shore A hardness, tensile strength, elongation at break and low tan d values (60 ° C. ) demonstrate

Die erfindungsgemäßen Kautschukmischungen zeigten keine Dispersionsprobleme. Bei der Verarbeitung wird wenig oder kein Anilin freigesetzt.The rubber mixtures according to the invention showed no dispersion problems. Little or no aniline is released during processing.

Claims (14)

  1. Rubber mixture comprising at most 1 phr of diphenylguanidine and at least
    - a non-polar rubber selected from the group consisting of NR, SBR, BR, IR, SIBR, IIR, ENR and EPDM, preferably NR, SBR, BR, IIR and EPDM, particularly preferably NR, BR and SBR,
    - a silica-based filler and/or carbon black,
    - a short-chain alkyl ester of glycerol according to formula (I)
    Figure imgb0004
     in which
    R1, R2, R3 are mutually independently hydrogen or a straight-chain or branched C1-C4-alkyl moiety, preferably a methyl moiety, and
    - 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane (CAS No.: 151900-44-6),
    where the total content of non-polar rubbers is at least 50 phr and the content of compounds of the formula (I) is from 0.1 to 40 phr.
  2. Rubber mixture according to Claim 1, characterized in that it comprises from 0.1 to 15 phr, preferably from 0.1 to 2 phr, and particularly preferably from 0.2 to 1 phr, of 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane (CAS No. 151900-44-6) .
  3. Rubber mixture according to either of Claims 1 and 2, characterized in that the total content of non-polar rubbers selected from the group consisting of NR, SBR, BR, IR, SIBR, IIR, ENR and EPDM, preferably from the group consisting of NR, SBR, BR, IIR and EPDM, particularly preferably from the group consisting of NR, BR and SBR is at least 60 phr, preferably at least 70 phr.
  4. Rubber mixture according to any of Claims 1 to 3, characterized in that it comprises polar rubbers, where the content of NBR, HNBR, HXNBR and XNBR is preferably in each case smaller than 10 phr, particularly preferably in each case smaller than 1.0 phr, more preferably in each case smaller than 0.1 phr and most preferably in each case smaller than 0.01 phr.
  5. Rubber mixture according to any of Claims 1 to 4, characterized in that it comprises at least one crosslinking agent, preferably at least one peroxidic or sulphur-based crosslinking agent, particularly preferably at least one crosslinking agent from the group comprising sulphur, dimorpholyl disulphide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulphide, dipentamethylenethiuram tetrasulphide (DPTT), tetramethylthiuram disulphide (TMTD) and tetrabenzylthiuram disulphide (TBzTD), very particularly preferably TBzTD.
  6. Rubber mixture according to any of Claims 1 to 5, characterized in that the content of compounds of the formula (I) is from 0.2 to 20 phr, preferably from 0.5 to 15 phr, particularly preferably from 1 to 12 phr, very particularly preferably from 2 to 10 phr and most preferably from 3 to 8 phr.
  7. Rubber mixture according to any of Claims 1 to 6, characterized in that it comprises from 50 to 100 phr of silica-based filler and from 0.2 to 12 phr of organic silanes, preferably sulphur-containing organic silanes, particularly preferably sulphur-containing organic silanes comprising alkoxysilyl groups and very particularly preferably sulphur-containing organic silanes comprising trialkoxysilyl groups.
  8. Rubber mixture according to any of Claims 1 to 7, characterized in that the compound of the formula (I) is used after ab- and/or adsorption on a carrier, preferably a carrier selected from the group comprising natural and synthetic silicates, in particular neutral, acidic or basic silica, aluminium oxide, carbon black and zinc oxide.
  9. Rubber mixture according to any of Claims 1 to 8, characterized in that the content of cellulose and/or cellulose derivatives is ≤ 1phr, preferably < 0.5 phr, particularly preferably < 0.1 phr and most preferably 0 phr.
  10. Process for the production of a rubber mixture according to any of Claims 1 to 9, characterized in that at least one rubber, one silica-based filler and/or carbon black and short-chain alkyl ester of glycerol according to formula (I) in Claim 1 are mixed with one another, at a temperature of from 40 to 200°C, preferably at from 80 to 150°C.
  11. Process for the production of rubber vulcanizates, characterized in that the rubber mixture according to any of Claims 1 to 9 is preferably vulcanized at a temperature of from 100 to 250°C, particularly preferably vulcanized at a temperature of from 130 to 180°C.
  12. Vulcanizates obtainable via vulcanization of rubber mixtures according to any of Claims 1 to 9.
  13. Rubber products, preferably tyres comprising one or more rubber vulcanizates according to Claim 12.
  14. Use of compounds of the formula (I) according to Claim 1 for the production of rubber mixtures according to any of Claims 1 to 9, of vulcanizates according to Claim 12 or of rubber products according to Claim 13.
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